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  • 2000-2004  (29)
  • 1985-1989  (3,938)
  • 1945-1949  (578)
  • Inorganic Chemistry  (3,993)
  • Genetics  (552)
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  • 1
    ISSN: 1432-198X
    Keywords: Key words Glomerulocystic kidney disease ; Oligohydramnion ; Renal failure-neonate ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Two newborns with glomerulocystic kidney disease manifesting as late onset oligohydramnion and neonatal anuria, yet without severe respiratory distress, are presented. They had a similar perinatal course and associated clinical manifestations. No associated congenital or inherited malformation syndrome could be defined. Both infants’ parents were first degree cousins and belonged to the same small Bedouin tribe, and neither they nor the infants’ siblings had polycystic kidneys or renal insufficiency, pointing to either a possible genetic etiology or a common external toxic exposure.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Intensive care medicine 26 (2000), S. S057 
    ISSN: 1432-1238
    Keywords: Key words Critical illness ; Intensive care ; Severity of illness ; Scoring systems ; Genetics ; Susceptibility ; Education
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Risk of critical illness is determined both by genetic and environmental influences, particularly those relating to infectious and cardiovascular diseases. Physiologically-based scoring systems cannot measure prior risk because they do not quantify physiological reserve independently of the acute illness. Genetic profiling could be useful for risk assessment. Early detection of critical illness involves identifying physiological ’triggers' for referral; this requires the education of nursing and medical staff in their significance. Analysis of the relationship between risk factors and interventions may need complex modelling techniques. Therapeutic strategies depend on the nature of the underlying problem: the most useful are likely to be those which enhance tissue oxygen delivery and resistance to infection.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    European journal of pediatrics 159 (2000), S. S35 
    ISSN: 1432-1076
    Keywords: Key words Obesity ; Genetics ; Child ; Nutrient balance ; Energy balance ; Environment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The epidemic diffusion of obesity in industrialised countries has promoted research on the aetiopathogenesis of this disorder. The purpose of this review is to focus mainly on the contribution that European research has made to this field. Available evidence suggests that obesity results from multiple interactions between genes and environment. Parents obesity is the most important risk factor for childhood obesity. Twin, adoption, and family studies indicated that inheritance is able to account for 25% to 40% of inter-individual difference in adiposity. Single gene defects leading to obesity have been discovered in animals and, in some cases, confirmed in humans as congenital leptin deficiency or congenital leptin receptor deficiency. However, in most cases, genes involved in weight gain do not directly cause obesity but they increase the susceptibility to fat gain in subjects exposed to a specific environment. Both genetic and environmental factors promote a positive energy balance which cause obesity. The relative inefficiency of self-adapting energy intake to energy requirements is responsible for fat gain in predisposed individuals. The role of the environment in the development of obesity is suggested by the rapid increase of the prevalence of obesity accompanying the rapid changes in the lifestyle of the population in the second half of this century. Early experiences with food, feeding practices and family food choices affect children's nutritional habits. In particular, the parents are responsible for food availability and accessibility in the home and they affect food preferences of their children. Diet composition, in particular fat intake, influences the development of obesity. The high energy density and palatability of fatty foods as well as their less satiating properties promotes food consumption. TV viewing, an inactivity and food intake promoter, was identified as a relevant risk factor for obesity in children. Sedentarity, i.e. a low physical activity level, is accompanied by a low fat oxidation rate in muscle and a low fat oxidation rate is a risk factor of fat gain or fat re-gain after weight loss. Conclusion Further research is needed to identify new risk factors of childhood obesity, both in the genetic and environmental areas, which may help to develop more effective strategies for the prevention and treatment of obesity.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    European journal of pediatrics 159 (2000), S. S183 
    ISSN: 1432-1076
    Keywords: Key words Database ; Genetics ; Information services ; Internet ; Mutation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Thanks to the World Wide Web, most results of research in genetics are made available in public databases. At the present time there are resources on genetic diseases, genes and their location, mutations of already cloned genes and on laboratories performing the mutation analysis. The main resources on phenotypes are On-line Mendelian Inheritance in Man (OMIM), Pedbase, GeneClinics, London Dysmorphology Database (LDDB) and Orphanet. The main resources on human genes are, in addition to OMIM, the Genome Database, Genatlas and Genecard. There are also two major sequence databases. All of them can be queried using the OMIM number of the disease. Central databases of mutations, as well as locus specific databases have been created. Their list is maintained at the Human Genome Organisation mutation database initiative website. Several initiative have been taken to integrate all these data and help the clinician to find out quickly what he/she needs. The website of the National Center for Biotechnology Information is the best example of such an effort with sections on diseases, a genome guide, and locus links. Several databases of genetic testing resources have been established. GeneTests is an on-line genetics resource that contains a directory of North American laboratories providing testing for heritable disorders. Orphanet is a similar database on French services which is in the process of becoming a European database. Conclusion Even if clinicians do not have as many services at their disposal as the molecular geneticists, various useful databases already exist and should no longer be ignored in practice.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    European journal of pediatrics 159 (2000), S. S208 
    ISSN: 1432-1076
    Keywords: Key words Cardiovascular disease ; Cystathionine β-synthase ; Genetics ; Methylenetetrahydrofolate reductase ; Mild hyperhomocysteinaemia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Over the last decade mild hyperhomocysteinaemia has widely been recognised as a new risk factor for arteriosclerosis and thrombosis. Main regulating enzymes of homocysteine (Hcy) metabolism are cystathionine β-synthase (CBS), methionine synthase and methylenetetrahydrofolate reductase (MTHFR). Early studies on patients with vascular disease described elevated Hcy concentrations after methionine loading and decreased CBS activity, resembling heterozygotes for CBS deficiency. Therefore, heterozygosity for CBS deficiency was proposed as the main cause of mild hyperhomocysteinaemia. However, more recent enzymatic and molecular genetic studies have demonstrated that heterozygosity for CBS deficiency is not or only a very minor cause of mild hyperhomocysteinaemia in vascular disease. We discovered two common genetic causes of mild hyperhomocysteinaemia, the 677C 〉 T and the 1298A 〉 C mutations in the coding region of MTHFR. The 677C 〉 T mutation causes reduced enzyme activity with thermolabile protein properties, elevated Hcy and low-normal or decreased plasma folate levels. The 1298A 〉 C mutation relates also to decreased enzyme activity, but not to thermolabile protein, and Hcy and folate levels are not influenced. However, compound heterozygosity for these two mutations, i.e. individuals with the 677CT/1298AC genotype, have elevated Hcy and decreased plasma folate levels. Gene-enviroment interactions between 677C 〉 T and folate is demonstrated in individuals with the 677TT genotype. Those with low-normal folate have elevated Hcy, whereas those with high-normal folate have normal Hcy concentrations. The elevated Hcy levels due to these mutations can be normalised by administration of folate, but whether folate reduces the risk of cardiovascular disease remains to be established. Conclusion Heterozygosity for cystathionine β-synthase deficiency is a minor cause of hyperhomocysteinaemia. The current data on mutations in the methylenetetrahydrofolate reductase gene do not tell us whether elevated plasma homocysteine plays a causal role in vascular disease. Low cellular vitamin status may be a possible cause and homocysteine may just be a marker for this situation.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1364-6753
    Keywords: Key words Parkinson's disease ; Familial Parkinson's disease ; Synuclein ; Parkin ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: ABSTRACT¶Parkinson's disease (PD) is a neurodegenerative disease with clinical features resulting from deficiency of dopamine in the nigrostriatal system. Most PD cases are sporadic and the primary cause of the disease is still unknown. Recently, familial PD and parkinsonism have received much attention because these forms of the disease might provide clues to the genetic risk factors involved in the pathogenesis of idiopathic PD. To date, two causative genes, α-synuclein and the parkin gene, have been identified. α-Synuclein is involved in the pathogenesis of an autosomal dominant form of PD and constitutes a major component of the Lewy body, which is a pathological hallmark of idiopathic PD. In addition, mutations in the parkin gene have been identified as the cause of autosomal recessive juvenile parkinsonism (AR-JP). AR-JP manifests itself as a highly selective degeneration of the substantia nigra and the locus coeruleus, but without Lewy body formation. In addition to these two genes, four chromosomal loci have been linked to other forms of familial PD. Furthermore, there are a number of other pedigrees of familial PD in which linkage to known genetic loci has been excluded. Molecular cloning of these disease genes and elucidation of the function of their gene products will greatly contribute to our understanding of the pathogenesis of idiopathic PD.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    The journal of headache and pain 1 (2000), S. S147 
    ISSN: 1129-2377
    Keywords: Key words Dopamine ; Migraine ; Genetics ; DRD2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Molecular genetics offers a novel approach to the understanding and management of migraine since the disorder is known to have a strong genetic component. In recent studies, polymorphisms in the genes for dopamine receptors have been evaluated. Both positive and negative association studies have been reported. In particular, these data suggest that activation of the DRD2 receptor plays a modifying role in the pathophysiology of migraine. As a result, existing data provide a molecular rationale for the documented efficacy of dopamine D2 receptor antagonists in the treatment of migraine. Therefore, at the present time, molecular genetic data provide support for the hypothesis that susceptibility to migraine may be modified, in part, by variations in dopamine DRD2 receptor function.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    The journal of headache and pain 1 (2000), S. S157 
    ISSN: 1129-2377
    Keywords: Key words Migraine ; Chronic tension type headache ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Pathophysiological studies have dominated migraine research for several years. However, these studies are difficult to interpret because it is difficult to decide whether the observed phenomena are primary or secondary to the migraine attack. For that reason it is important that future migraine research focus on studies that concern migrain etiology. Migraine is a paroxysmal disorder. It is most likely and ion-channel disorder like familial hemiplegic migraine. The present paper focuses on genetic factors in migraine and chronic tension-type headache.
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  • 9
    ISSN: 1129-2377
    Keywords: Key words Cluster headache ; Familial occurrence ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract A Danish genetic study showed increased risk of cluster headache (CH) among relatives of CH patients. We studied the families of 191 CH patients (118 males, 73 females; mean age 45.9 years) attending the Milan Headache Center. Information on 3589 relatives was collected by direct interview of the probands (n = 118) or by mailed questionnaire (n = 73). The diagnostic criteria of the IHS were used. A positive family history was found in 19% (37 of 191) of the families. A total of 32 first-degree (32 of 1036, 3.1%) and 15 second-degree (15 of 2553, 0.6%) relatives were affected. The relative risk of CH was 26.89 (95% CI, 17.57–36.21) in the first-degree relatives and 4.35 (95% CI, 2.13–5.21) in second-degree relatives. This study shows increased familial risk of cluster headache in an Italian population and confirms that cluster headache is, in some families, and inherited disorder.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    The journal of headache and pain 1 (2000), S. S135 
    ISSN: 1129-2377
    Keywords: Key words Migraine ; Headache ; Genetics ; Serotonin ; Dopamine ; Mitochondria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Migraine carries a significant hereditary determination. Familial hemiplegic migraine (FHM) has been recently linked to mutations in the CACNA1A gene on chromosome 19. CACNA1A codes for a subunit of a neural calcium channel. Other linkage loci on chromosome 1q21-23 and 1q31 have been reported. Several linkage and association studies have been performed to determine the role of the CACNA1A gene, and of other candidate genes implicated in the metabolism of serotonin and dopamine, in the more common types of migraine. Co-morbidity of migraine with vascular events has been analysed versus genetic prothrombotic factors and mitochondrial DNA, and genes involved in the inflammatory cascade have been explored. Though no definite conclusions have emerged from these studies as yet, molecular genetics of migraine can be expected to unravel the complex aetiologies of these fascinating diseases.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    The journal of headache and pain 1 (2000), S. S153 
    ISSN: 1129-2377
    Keywords: Key words Migraine ; Genetics ; Dopamine ; Hypersensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Migraine is a common chronic disorder with an etiology still mostly unknown. Several neurotransmitters such as dopamine and serotonin are considered to be involved in the pathogenesis of the disease and the study of their systems is crucial in the understanding of migraine. Dopaminergic receptors are variously represented in human CNS and periphery. The hypothesis that a hypersensitivity of the dopaminergic system may have a role in migraine is based on clinical and genetic data. Genetic data are represented by association studies using dopaminergic genes as candidate genes which show that the D2 receptor gene appears to be involved in the pathogenesis of migraine.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    The journal of headache and pain 1 (2000), S. S141 
    ISSN: 1129-2377
    Keywords: Key words Migraine ; Genetics ; Human leukocyte antigens ; Heredity ; Susceptibility
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Human leukocyte Antigens (HLA) are encoded by genes located on chromosome 6p21. Genes important in migraine are being recognized in two basic ways: association studies and linkage analysis. One of the strongest associations is with the HLA region. Actually, genome scan studies suggest that multiple genes are involved in both migraine without aura (MWoA) and migraine with aura (MWA). However, both MWoA and MWA are disorders in which multiple factors, including environmental and genetic factors, confer disease susceptibility. Linkage analysis is identifying new candidate genes that will help to explain the etiology of migraine. In this review previous studies regarding genetic susceptibility to migraine are analyzed, particularly those related to the HLA region. I discuss evidence that HLA shared-hyplotypes in MWoA-affected pairs in different than that expected, that HLA-DR2 antigen provides additional basis for the proposed genetic heterogeneity between MWoA and MWA, and lastly that TNFB gene studies seem to play an important role in the susceptibility to MWoA. In the past years, major advances hae been made in understanding the genetic foundation of MWoA and MWA. Our reported genome-scan studies support the concept that MWoA/MWA are coinherited with a particular HLA region. However, the examination of candidate genes (Ca2+ channel, vascular, CNS, etc.) in a large migraine population seems to be the correct direction in which we have to move. More MWoA/MWa gene studies are needed to test this developing hypothesis and to further establish the complete genetic scenario of migraine.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 100 (2000), S. 401-408 
    ISSN: 1432-2242
    Keywords: Key words Complementary genes ; Extreme virus resistance ; Genetics ; Necrotic tubers ; Restricted virus distribution ; Solanum tuberosum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The potato cultivar ’Shepody’ is susceptible to a number of potato viruses including potato virus Y (PVY, potyvirus) but was found to possess extreme resistance to another potyvirus, potato virus A (PVA). ’Shepody’ plants were resistant to PVA infection in manual and graft inoculations. PVA replication was not detected in any of the inoculated plants by ELISA, an infectivity assay and RT-PCR. However, ’Shepody’ plants grafted with shoots containing PVA developed a novel symptomology which resembled a virus infection in appearance and in rate of translocation to the entire plant. Efforts to transmit the symptom-inducing agent manually failed. Graft-inoculation to potato virus indicator plants and PVA-susceptible potato plants showed that the symptom inducer was PVA at an extremely low concentration, detected using RT-PCR followed by Southern blot assay. Tubers from grafted but resistant ’Shepody’ plants had necrotic surfaces and internal spots. PVA was detected from necrotic areas but not from the non-necrotic ones. However, plants resulting from necrotic tubers were free from aerial leaf symptoms observed in grafted plants and produced non-necrotic normal tubers. A trace-back of the parental lineage of ’Shepody’ indicated that the resistance had been introgressed from the cultivar ’Bake King’. Analysis of progeny of a cross of resistant ’Shepody’ to the susceptible ’Goldrus’ indicated that this resistance is controlled by two independent dominant complementary genes in contrast to monogenic resistance reported for other potato viruses.
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  • 14
    ISSN: 1432-2242
    Keywords: Key words Avicennia marina ; Microsatellite ; Mangrove ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  An enriched microsatellite library of the mangrove species Avicennia marina was constructed, in which 85.8% of the clones contained microsatellite sequences. Of the microsatellite repeat sequences isolated, 55.0% were di-nucleotides, 34.2% were tri-nucleotides, 50.0% were perfect, 24.2% were imperfect, and 15.0% were compound. Four different di-nucleotide repeats were isolated with repeat lengths ranging from 5 to 33; ten different tri-nucleotide repeats were isolated with repeat lengths ranging from 3 to 25. The most common di-nucleotide was the AC/TG repeat; the most common tri-nucleotide was the CCG/GGC repeat. Sixteen microsatellite sequences were selected for primer design, and 6 primers were selected to investigate the polymorphism detected among 15 individuals of A. marina from three natural populations in Australia. A total of 40 alleles were detected at 6 microsatellite loci. The number of alleles per microsatellite locus ranged from 5 to 13. On average, 7 alleles were detected per locus. All microsatellite loci showed high levels of gene diversity (heterozygosity), with values ranging from 0.53 to 0.88; the mean value of gene diversity was 0.70. Microsatellite loci were also tested for conservation across Avicennia species. There was a decline in amplification success with increasing divergence between Avicennia species. The results indicate that microsatellites are abundant in the Avicennia genome and can be valuable genetic markers for assessing the effects of deforestation and forest fragmentation in mangrove communities, which is an important issue for mangrove conservation and afforestation schemes.
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 101 (2000), S. 234-240 
    ISSN: 1432-2242
    Keywords: Key words Cherry ; Genetics ; Compatibility ; Incompatibility ; Isoelectric focusing ; Prunus avium ; Ribonuclease
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The (in)compatibility genotypes of two self-compatible sweet cherry selections, JI 2420 and JI 2434, originating from the John Innes Institute were re-examined. The selections and seedlings derived from them were analysed for stylar ribonucleases, which are known to correlate with S alleles, and the outcome of test crosses was recorded. JI 2420, which had been reported previously as S 3 S 4 ", where " indicates loss of pollen activity, was deduced to have the genotype S 4 S 4 ’. For JI 2434, which had been reported previously as S 3 S 4 0 , S 3 S 3 0 or S 3 S 3 ", where 0 indicates loss of pollen and stylar activity, two different clones were identified. One, at East Malling, was deduced to be S 3 "S 4 ; the other, at Ahrensburg, appeared to be S 3 S 3 " or S 3 S 3 0 .
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  • 16
    ISSN: 1432-1211
    Keywords: Key words Skin ; Genetics ; TNFA ; ¶Inflammation ; PCR-RFLP
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  Mechanisms underlying susceptibility to skin irritants are not clearly understood. Cytokines play a key role in inflammation, and functional polymorphisms in cytokine genes may affect responses to irritants. We investigated the relationship between polymorphism in the tumor necrosis factor (TNF) α-chain gene and responses to irritants. Volunteers (n=221) tested with sodium dodecyl sulfate (SDS) and benzalkonium chloride (BKC) were divided into responders and nonresponders and high and low irritant-threshold groups. DNA was assayed for the TNF-308 polymorphism by a polymerase chain reaction-restriction fragment length polymorphism method. There was a significant increase in the A allele (P=0.030) and AA genotype (P=0.023) in both the SDS low irritant-threshold group and in SDS responders (A allele P=0.022, AA genotype P=0.048). In the BKC low irritant-threshold group, we found a significant increase in the A allele (P=0.002) and AA genotype (P=0.016). Individuals with a low threshold to both irritants demonstrated a significant increase (P=0.002) in the A allele. This is the first description of a nonatopic genetic marker for irritant susceptibility in normal individuals. Genotyping for theTNF-308 polymorphism may thus contribute to screening of individuals deemed at risk of developing irritant contact dermatitis.
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  • 17
    ISSN: 1432-1459
    Keywords: Key words Progressive ¶supranuclear palsy ; Genetics ; Clinical characteristics ; Parkinsonism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Genetic studies have detected an association between the presence of the τ gene A0 allele and patients with progressive supranuclear palsy (PSP). This study examined whether patients with this polymorphism exhibit distinct demographic or clinical characteristics. We studied 26 patients who fulfilled clinical criteria for the diagnosis of PSP, 20 who had the A0/A0 genotype and 6 who had other genotypes. A questionnaire on demographic data, past medical history, familial history, and initial symptoms was completed as part of the consultation. A complete neurological examination was performed and PSP symptoms were quantified following Golbe’s PSP disability scale. We found a significant difference in the age at onset of PSP symptoms, which was 65.9 ± 5.3 years in the A0/A0 group and 71.2 ± 5.6 in the non-A0/A0 group (P = 0.016). There were no significant differences in the years from disease onset between the two groups. Symptom severity did not differ significantly in patients with the different A0/A0 genotypes. The detection of significantly lower age at onset with the A0/A0 alleles is consistent with the known association of this genotype as a risk factor for PSP. No significant differences were detected in symptom severity between the two groups of patients.
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  • 18
    ISSN: 1432-1459
    Keywords: Key words Amyotrophic lateral sclerosis ; Genetics ; Presenilin-1 intron 8 polymorphism ; Apoptosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The mechanisms underlying motor neuron degeneration in amyotrophic lateral sclerosis are not fully understood. Recent studies suggest that apoptosis is involved in the abnormal neural death that occurs in this devastating disease. Presenilin-1, a transmembrane protein, seems to be implicated in apoptosis. To determine whether presenilin-1 intron 8 polymorphism has an influence in the course of amyotrophic lateral sclerosis, we examined this polymorphism genotypes in a large group of patients (n=72) with amyotrophic lateral sclerosis and in a random sample of 213 healthy individuals. The results showed a significant difference in genotype (P 〈 0.04) and allele (P 〈 0.03) distribution between patients and controls. These results suggest a possible intervention of presenilin-1 in the pathogenesis of amyotrophic lateral sclerosis.
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  • 19
    ISSN: 1432-1459
    Keywords: Key words Parkinson’s disease ; Monoamine oxidase B ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Monoamine oxidase B (MAOB) metabolises dopamine and activates neurotoxins known to induce parkinsonism in humans and primates. Therefore the MAOB gene (MAOB; Xp15.21–4) is a candidate gene for Parkinson’s disease (PD). Longer length dinucleotide repeat sequences in a highly polymorphic GT repeat region of intron 2 of this gene showed an association with PD in an Australian cohort. We repeated this allele-association study in a population of 176 Chinese PD patients ¶(90 men, 86 women) and 203 age-matched controls (99 men, 104 women). Genomic DNA was extracted from venous blood and the polymerase chain reaction was used to amplify the appropriate regions of the MAOB gene. The length of each (GT) repeat sequence was determined by 5% polyacrylamide denaturing gel electrophoresis. There was no significant difference in allele frequencies of the (GT) repeat allelic variation between patients and controls (χ2 = 2.48; df = 5, P 〈 0.75). Therefore the longer length GT repeat alleles are not associated with PD in this Chinese population. Possible reasons for the discrepancy between Chinese and Australian populations include a different interaction between this genetic factor and environmental factors in the two populations and the possibility that the long length GT repeat alleles may represent a marker mutation, genetically linked to another susceptibility allele in whites but not in Chinese. Methodological differences in the ascertainment of cases and controls in this cohort could also explain the observed differences. Further study is required to determine whether the longer length GT repeat alleles are true susceptibility alleles in PD.
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  • 20
    ISSN: 1432-1459
    Keywords: Key words Multiple sclerosis ; Genetics ; ICAM-1 gene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract An increased amount of the intercellular adhesion molecule (ICAM) 1 molecule has been found in the blood of actively relapsing multiple sclerosis (MS) patients, but is unclear whether this enhanced expression is partially causative of the MS process, or whether it is merely an epiphenomenon of the inflammatory-immunological reaction. Using the transmission disequilibrium test (TDT), we studied exon 4 and exon 6 polymorphism of the ICAM-1 gene from 157 families with both parents, one affected and one healthy sib coming from Sardinia, an Italian island having a high incidence and prevalence of MS. TDT did not show variation in the expected 50:50 frequency in transmission in either healthy or affected sibs, using phenotypic or genotypic analysis. Moreover, independence from the predisposing HLA-DRB1-DQA1-DQB1 haplotype was confirmed by TDT analysis performed on the patients stratified according to the presence or absence of the HLA-DRB1, DQA1, DQB1 Sardinian predisposing haplotypes. Our data suggest that the increased expression of the ICAM-1 molecule observed in both blood and periplaque microvessels may be considered a consequence of the inflammatory process rather than the result of a genetic variation.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neurology 247 (2000), S. 81-87 
    ISSN: 1432-1459
    Keywords: Key words Dementia ; Vascular ¶dementia ; Alzheimer’s disease ; Risk factors, stroke ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract This review describes differing profiles of vascular risk factors in different types of dementia. Although vascular risk factors are related to various types of strokes, their independent effect on the occurrence of poststroke dementia appears to be small. Various risk factors have been identified for microangiopathy-related cerebral abnormalities, such as white matter changes and lacunae, which are the core lesions for the development of a vascular dementia syndrome without stroke symptoms. Most consistently, arterial hypertension and diabetes mellitus have been found to be associated with such brain abnormalities. Diastolic blood pressure seems to be of particular importance as recent investigations demonstrate that this factor is related to the course of multiple lacunar strokes and the progression of white matter disease. Epidemiological studies report that various vascular risk factors including arterial hypertension, diabetes mellitus, and atrial fibrillation may also be associated with Alzheimer’s disease. There is also evidence of a direct relationship between Alzheimer’s disease and general atherosclerosis. Further investigations are needed to determine whether these associations are due to the weakness of diagnostic criteria, or whether vascular risk factors indeed modulate the clinical expression of primary degenerative dementia. Common susceptibility genes leading to shared risk factors may be one of the reasons for a higher coincidence of Alzheimer’s disease and vascular dementia than can be expected by chance. A modulatory effect of vascular risk factors in the development of primary degenerative dementia may extend treatment options.
    Type of Medium: Electronic Resource
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  • 22
    ISSN: 1432-1459
    Keywords: Key words Multiple sclerosis ; Siblings ; Genetics ; Oligoclonal bands ; Measles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We found that 19% (9/47) of healthy siblings of patients with clinically definite multiple sclerosis had an intrathecal immunological reaction with two or more 2 CSF-enriched oligoclonal bands (OCBs), in contrast to (4%) (2/50) unrelated healthy controls. Furthermore, in this group of nine healthy sibs the measles CSF IgG antibody titers were higher than that of the other sibs and that of controls. There were also differences in the serum titers for measles IgG antibody, which were higher in the group of all healthy sibs than in healthy volunteers, and (as with CSF titers) higher in the subgroup of healthy sibs with two or more 2 CSF-enriched OCBs than the other sibs. Thus a significant proportion of healthy siblings to MS patients have a partially hyperimmune condition similar to that occurring in MS, which in 19% manifested itself as an OCB reaction, in 9% as increased CSF measles IgG antibody titers, and in 21% as increased serum measles IgG antibody titers, these phenomena tending to occur in the same individuals. This condition is characterized by CSF-enriched OCBs with undefined specificity, although some increased antiviral reactivity is found both in the serum and CSF. While it needs further characterization, a genetic trait interacting with common infections is suggested. The recurrence risk of this condition is approximately five times higher than the 3–4% recurrence risk for manifest MS reported for sibs.
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  • 23
    ISSN: 1433-8491
    Keywords: Key words Dopamine receptor D4 ; Genetics ; Personality inventory ; Polymorphism ; Excitement-Seeking
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract An association between long alleles of a variable number tandem repeat (VNTR) polymorphism in the dopamine receptor D4 gene and the extraversion related personality traits Excitement and Novelty Seeking has been reported in healthy subjects. In an attempt to replicate the previous findings, 256 healthy Caucasian volunteers were analysed for a potential relationship between the dopamine receptor D4 exon III VNTR polymorphism and Extraversion as assessed by the Revised Neo Personality Inventory (NEO PI-R). The present study did not yield evidence for an association between Extraversion and the dopamine receptor D4 polymorphism.
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  • 24
    ISSN: 1433-8491
    Keywords: Key words Pharmacogenetics ; Genetics ; Risk factor ; Choreoathetotic movements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract In the search for genetic factors contributing to tardive dyskinesia, dopamine receptor genes are considered major candidates. The dopamine D3 receptor is of primary interest as dopamine D3 receptor knock-out mice show locomotor hyperactivation resembling extrapyramidal side-effects of neuroleptic treatment. Furthermore, Steen and colleagues (1997) recently reported an association between tardive dyskinesia and a dopamine D3 receptor gene variant. In the present study we tried to replicate this finding. We investigated 157 patients with schizophrenia or schizoaffective disorder receiving long-term neuroleptic medication who never or persistently displayed tardive dyskinesia. As advanced age is a main risk factor for tardive dyskinesia, we also compared older patients with a long duration of schizophrenia not displaying tardive dyskinesia to younger patients with a shorter duration of the illness displaying tardive dyskinesia. However, we found no evidence that the dopamine D3 receptor gene is likely to confer susceptibility to the development of tardive dyskinesia.
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  • 25
    ISSN: 1590-3478
    Keywords: Key words Nervous system ; Cavernous angiomas ; Genetics ; Onset symptoms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We performed a clinical and genetic study of patients affected by cavernous angiomas (CA) of the nervous system. We examined initial signs and symptoms in sporadic and familial cases. We obtained clinical, neuroimaging and genetic data on 15 Italian patients with CA of the nervous system with positive, doubtful or apparently negative family history. Genetic markers surrounding three different gene regions (7q, 3q and 7p) were analysed. In one small family, genetic linkage was consistent with all chromosome loci. In another family with the unusual association of cerebral and spinal CA, linkage with chromosome 7q and, likely, 7p was excluded, while linkage with locus 3q was possible. Our results indicate that Italian families with CA may show genetic heterogeneity. Non-specific and subtle onset symptoms hide the presence of CA within families. Patients with multiple CA may have silent cerebral lesions confirming the low penetrance of clinical signs in spite of radiological ones.
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  • 26
    ISSN: 1590-3478
    Keywords: Key words Evoked potentials ; Ceroid lipofuscinoses ; Mutation ; Classification ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The importance of visual evoked potential (VEPs) and electroencephalography for diagnosing and distinghishing the infantile (INCL), late-infantile (LINCL) and juvenile (JNCL) forms of neuronal ceroid lipofuscinoses (NCL) is well established. Variant forms with protracted clinical courses and atypical symptoms have been described recently, whose neurophysiological characteristics sometimes overlap those of LINCL and JNCL. It is unclear whether these variant forms are due to phenotypic variability of known genetic defects, or represent new mutations. Twenty-eight NCL patients have been diagnosed at our institute; a proportion of them were investigated genetically. In 17 we performed neurophysiological investigations including VEPs, brainstem auditory (BAEP) and upper limb somatosensory (SEP) evoked potentials. We found typical and diagnostic electrophysiological involvement of the visual system in 8 patients with classic forms of NCL. Furthermore, the distinctive features of the multimodal evoked potentials in most of the six patients with variant NCL suggest that these are distinct genetic entities.
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  • 27
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    Neurological sciences 21 (2000), S. 373-377 
    ISSN: 1590-3478
    Keywords: Key words Myoclonus-dystonia ; Essential myoclonus ; Dystonia ; Alcohol ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We present the clinical profile of a group of patients with myoclonus and dystonia sensitive to alcohol and address these cases in the context of essential myoclonus. Six patients from 4 families were selected: 4 men and 2 women with myoclonus affecting predominantly the arms. Active movements of these segments elicited the dystonic and myoclonic movements. A marked improvement with alcohol intake was seen. Laboratory findings including EEG, SSEP, and cranial CT and MRI were normal. Surface EMG recording showed bursts with duration of 30–112 ms in 3 patients. One patient showed a triphasic recording pattern (agonist-antagonist-agonist) of ballistic type. Our findings suggest that the myoclonus-dystonia disorder is present in Brazilian patients.
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  • 28
    ISSN: 1437-2320
    Keywords: Key words Von Hippel-Lindau disease ; Hemangioblastoma ; Endolymphatic sac tumor ; Angiogenesis ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  Von Hippel-Lindau disease (VHL) is a hereditary cancer syndrome caused by germline mutations of the VHL tumor suppressor gene. Major progress has been made in the last decade in both clinical and fundamental aspects of VHL. The VHL gene product, pVHL, has major and multiple functions: pVHL regulates not only first angiogenesis but also extracellular matrix formation and the cell cycle. A molecular diagnosis of VHL is now available, leading to a transformation in clinical management of patients and their families. Diagnosis of VHL has to be suspected in patients with a VHL-related tumor without familial history and especially in case of hemangioblastoma or endolymphatic sac tumors. Such patients should be systematically investigated for clinical and molecular evidence of VHL disease. Treatment of symptomatic hemangioblastomas remains mainly neurosurgical, often in emergency, but stereotactic radiosurgery is emerging as an alternative therapeutic procedure. In the future, antiangiogenic drugs could represent a potential medical treatment of CNS hemangioblastomas in view of their highly vascular structure. Lastly, visceral manifestations of VHL disease are also of critical importance and require early detection for effective treatment.
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  • 29
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    Child's nervous system 16 (2000), S. 809-820 
    ISSN: 1433-0350
    Keywords: Keywords Pediatric neurosurgery ; Molecular biology ; Genetics ; Novel therapeutics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  The new millennium beckons for novel advances in the diagnosis and treatment of pediatric neurosurgical conditions. Almost every aspect of pediatric neurosurgery has changed over the last decade. Undoubtedly with the application of knowledge in molecular biology to human disease many aspects of neurosurgery, especially neuro-oncology and the field of neuro-developmental anomalies, will change appreciably over the next decade. Overall, the trend in surgery in general and neurosurgery in particular is toward less invasive procedures and possibly non-surgical interventions. This review will briefly cover many of the important areas of pediatric neurosurgery. We will describe the state-of-the-art of our subspecialty and discuss possible future directions.
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  • 30
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    Psychopharmacology 99 (1989), S. 147-150 
    ISSN: 1432-2072
    Keywords: Locomotor activity ; CNS depression ; Cocaine ; Mice ; Behavior ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Cocaine produces several behavioral effects, most notably locomotor stimulation. Biochemically, cocaine is known to inhibit reuptake at the three monoamine transporter sites, and may have highest affinity at the serotonin transporter. Serotonin augmentation has been associated with decreases in behavioral activity, but cocaine has not been reported to produce behavioral depressant effects except at high doses which cause stereotypy and disruption of behavior. This study examined the effects of relatively low doses of cocaine, in the range of 0.1–10 mg/kg, on locomotor activity in C57BL/6J and DBA/2J mice. A biphasic dose-response curve was seen for both strains. At the lowest doses, activity was depressed. As the dose of cocaine increased, activity returned to baseline, and at the highest doses, increases in locomotor activity were found. DBA/2J mice were depressed at a lower dose of cocaine than were C57BL/6J mice; however, C57BL/6J mice showed locomotor depression over a broader range of doses. Activity was maximally depressed at 0.1 mg/kg for DBA/2J mice, and maximally depressed at 0.3 mg/kg for C57BL/6J mice. Thus, low doses of cocaine are shown to produce significant decreases in locomotor activity in two strains of mice. It is postulated that these low doses of cocaine which depress locomotor activity do so via inhibition of serotonin uptake, resulting in potentiation of serotonergic activity.
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  • 31
    ISSN: 1432-2072
    Keywords: Ethanol ; Bicuculline ; Picrotoxin ; Seizures ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The convulsant potency of bicuculline, a GABA antagonist, was shown to be greater in Short-Sleep (SS) mice than in Long-Sleep (LS) mice. LS mice, selectively bred for lengthy ethanol-induced narcosis, had longer latencies to myoclonus and clonus following administration of bicuculline and picrotoxin than did ethanol-resistant SS mice. SS mice were also more susceptible to pentylenetetrazol-induced myoclonus, but not clonus. F1 hybrids showed bicuculline seizure sensitivity intermediate to the two parent lines. Ethanol weakly inhibited bicuculline-induced myoclonus in both LS and SS mice. Clonus was clearly antagonized by ethanol in both lines, but to a similar degree. These data provide evidence for a GABAergic role in geno-type-dependent sensitivity to ethanol.
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  • 32
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    Psychopharmacology 98 (1989), S. 518-523 
    ISSN: 1432-2072
    Keywords: Ethanol ; GABA ; Bicuculline ; Sedation ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Two lines of mice, selectively bred for differential sensitivity to the soporific effects of ethanol (ETOH), were administered GABAergic drugs in an effort to evaluate a role for GABA in ETOH sensitivity. ETOH sensitive Long-Sleep mice (LS) showed potentiated ETOH sedation when administered bicuculline, muscimol and aminooxyacetic acid (AOAA). ETOH-insensitive SS mice exhibited reduced ETOH sedation in the presence of the antagonists, bicuculline and picrotoxin, and potentiated sedation in the presence of muscimol and AOAA. These changes in narcosis duration were interpreted as central effects, since blood ethanol levels at waking from ETOH sedation varied with GABAergic drug treatment. Picrotoxin antagonized pentobarbital-induced nacrosis in both lines, but to a greater extent in SS mice. These and other experiments with a genetically heterogeneous stock suggest GABA involvement in genotype-dependent ETOH sensitivity, but do not support a simple role of GABA receptor involvement.
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  • 33
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    Psychopharmacology 98 (1989), S. 549-555 
    ISSN: 1432-2072
    Keywords: Ethanol (ETOH) ; GABA ; Bicuculline ; Sedation ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Genetic influences on the interaction between ethanol (ETOH) and gamma-aminobutyric acid (GABA) neurotransmitter systems were eveluated with a survey of responses to coadministration of ETOH and a GABA antagonist, bicuculline, in a battery of inbred mouse strains. The selectively bred ETOH-sensitive Long-Sleep (LS) mice, the relatively ETOH-resistant Short-Sleep (SS) mice, and a genetically heterogeneous stock (GHS) were also evaluated. The effect of bicuculline on ETOH-induced sedation, hypothermia, and blood ethanol content upon recovery from sedation was assessed. Inheritance of these responses was also examined using F1 hybrids. The effect of bicuculline on ETOH-produced narcosis varied widely among stocks and included antagonism, potentiation, and no effect. Changes in ETOH-induced narcosis produced by bicuculline were accompanied by changes in blood ethanol concentrations consistent with an hypothesis of altered central nervous system sensitivity to ETOH. Knowledge of a strain's seizure susceptibility to the GABA antagonist or of its sensitivity to the hypnotic effects of ETOH were of no predictive value in estimating the outcome of coadministration studies, suggesting at least partially separate genetic influences on each phenotype. In cross-breeding studies there was commonly dominance toward a profile of bicuculline antagonism of ETOH narcosis but different patterns of dominance were observed for seizure susceptibility, again inicating separate genetic control. The results suggest considerable complexity of GABAergic involvement in genotype-dependent ETOH sensitivity.
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  • 34
    ISSN: 1432-2242
    Keywords: Solanum tuberosum ; Genetics ; Breeding ; Plant appearance ; Economy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary In 1985, 1986 and 1987, 600 clones were visually assessed at harvest on plant appearance. The clones were harvested 80 days after planting in the first year, in the following years after approximately 80 days as well as after 145 days. The correlation coefficients between years and between harvest times were low to medium. Simulating different selection intensities using the performance of these 600 clones in two successive years, the relation between selection pressure in the first year and the retained proportion of well performing clones in the second year was described. Including the costs of testing, the most economic selection procedure was calculated. This procedure consisted in testing 1,579 first-year clones and 499 second-year clones for every 100 third-year clones required. The optimal period of the main evaluation in the second clonal year is at ware potato harvest time. This selection procedure also provides good selection possibilities for underwater weight and foliage maturity.
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  • 35
    ISSN: 1432-1939
    Keywords: Logging disturbance ; Land gastropods ; Ecology ; Genetics ; Population
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Ecological and genetic properties of two North American terrestrial gastropods (Mesomphix spp.) were characterized in paired control and previously logged watersheds in two North Carolina forests (Coweeta and the Great Smoky Mountains National Park) of the Southern Appalachian Biosphere Reserve Cluster. Shell growth was greater in the control sites, but density and mortality were largely independent of prior logging history and forest reserve. Based on starch gel electrophoresis data, both species showed their highest levels of genetic diversity in the Coweeta forest, the component of the reserve cluster which had the most extensive and variable history of logging disturbance. M. subplanus also exhibited higher levels of heterozygosity in logged than in control watersheds, and M. andrewsae showed over twice as many rare alleles in disturbed sites as in control sites. F-statistic analysis depicted both excess levels of homozygosity and moderate genetic differentiation among the populations, reflecting the effects of small population size and perhaps drift and inbreeding. Estimated gene flow was relatively low. These results correspond to the recent finding by Bryant et al. (1987) and others on the effects of bottlenecks, and to the contrasting history of habitat instability of the two major study forests.
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  • 36
    ISSN: 1432-0428
    Keywords: Genetics ; insulin gene ; DQβ gene ; fibrocalculous pancreatic diabetes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Fibrocalculous pancreatic diabetes (previously known as tropical pancreatic diabetes) is a rare cause of diabetes confined to countries within the tropical belt. The aetiology of fibrocalculous pancreatic diabetes is thought to be environmental although the agent(s) is unknown. We have investigated a possible genetic basis of this disease by looking for restriction fragment length polymorphisms of genes implicated in the aetiology of diabetes mellitus. Seventy-six Dravidian patients with fibrocalculous pancreatic diabetes were studied, and the restriction fragment length polymorphisms obtained compared to racially matched control subjects (n=94), patients with Type 2 (non-insulin-dependent) diabetes (n=87) and Type 1 (insulin-dependent) diabetes (n=58). No association of fibrocalculous pancreatic diabetes was found with restriction fragment length polymorphisms of the insulin receptor gene. Although no association of fibrocalculous pancreatic diabetes was found with polymorphism of the HLA DRα/DQα/DXα genes, an association was found with the Taq 1 restriction fragment length polymorphisms of the DQβ gene (DQβ T2/T6 present in 39% of patients with fibrocalculous pancreatic diabetes compared to 19% in control subjects; p=0.01; corrected p value=0.04) which is similar to that found in Type 1 but not Type 2 diabetes. An association of fibrocalculous pancreatic diabetes was also found with the hypervariable region in the 5-prime flanking region of the insulin gene; 40% of patients possessed the class 3 allele compared to 9.5% of control subjects p=0.0001; corrected p value=0.0008). In Type 2 diabetes, similar results were obtained with 33% subjects possessing the class 3 allele (p value compared to control subjects=0.0005; corrected p value=0.004). This study suggests that fibrocalculous pancreatic diabetes has a genetic component in its aetiology. Furthermore, its origin might be related to an individual with part of the genetic predisposition to diabetes (Type 1 or Type 2) who additionally has evidence of chronic calcific pancreatitis.
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  • 37
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    Archives of microbiology 152 (1989), S. 335-341 
    ISSN: 1432-072X
    Keywords: Carboxydotrophic bacteria ; Plasmids ; CO dehydrogenase subunits ; N-terminal sequences ; Oligonucleotides ; Hybridization ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The 17 (S), 30 (M) and 87 kDa (L) subunits of CO dehydrogenases from the CO-oxidizing bacteria Pseudomonas carboxydoflava, Pseudomonas carboxydohydrogena and Pseudomonas carboxydovorans OM5 were isolated and purified. The N-terminal sequences of same subunits from different bacteria showed distinct homologies. Dot blot hybridization employing oligonucleotide probes derived from the sequences of the S-subunit of P. carboxydovorans OM5 and the M-subunit of P. carboxydohydrogena and DNA of the plasmid-containing CO-oxidizing bacteria Alcaligenes carboxydus, Azomonas B1, P. carboxydoflava, P. carboxydovorans OM2, OM4 and OM5 indicated that all genes encoding these subunits reside on plasmids. That in P. carboxydovorans OM5 CO dehydrogenase structural genes are located entirely on plasmid pHCG3 was evident from the absence of hybridization employing DNA from the cured mutant strain OM5-12. CO dehydrogenase structural genes could be identified on the chromosome of the plasmid-free bacteria Arthrobacter 11/x, Bacillus schlegelii, P. carboxydohydrogena and P. carboxydovorans OM3. There was no example of a plasmid-harboring carboxydotrophic bacterium that did not carry CO dehydrogenase structural genes on the plasmid. The N-terminal sequences of CO dehydrogenase structural genes were found to be conserved among carboxydotrophic bacteria of distinct taxonomic position, independent of the presence of plasmids. It is discussed whether this might be the consequence of horizontal gene transfer.
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  • 38
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    Theoretical and applied genetics 78 (1989), S. 97-104 
    ISSN: 1432-2242
    Keywords: Beta vulgaris ; Sugar beet ; Isozymes ; Genetics ; Linkage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Five isozyme systems were genetically investigated. The different separation techniques, the developmental expression and the use as marker system in sugar beet genetics and breeding is discussed. Isocitrate dehydrogenase was controlled by two genes. The gene products form inter- as well as intralocus dimers, even with the gene products of the Icd gene in B. procumbens and B. patellaris. Adenylate kinase was controlled by one gene. Three different allelic forms were detected, which were active as monomeric proteins. Glucose phosphate isomerase showed two zones of activity. One zone was polymorphic. Three allelic variants, active as dimers, were found. Phosphoglucomutase also showed two major zones of activity. One zone was polymorphic and coded for monomeric enzymes. Two allelic forms were found in the accessions studied. The cathodal peroxidase system was controlled by two independent genes, of which only one was polymorphic. The gene products are active as monomers. Linkage was found between red hypocotyl color (R) and Icd 2. Pgm 1, Gpi 2, Ak 1 and the Icd 2-R linkage group segregated independently.
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  • 39
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    Journal of molecular medicine 67 (1989), S. 225-237 
    ISSN: 1432-1440
    Keywords: Atherosclerosis ; Apolipoprotein ; Gene expression ; Genetics ; Evolution ; Gene duplication ; Lipid binding ; DNA polymorphism ; Hypercholesterolemia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The plasma apolipoproteins can be classified into two subgroups: the soluble apolipoproteins including apolipoprotein (apo) A-I, A-II, A-IV, C-I, C-II, C-III, and E, and the apoBs including apoB-100 and apoB-48. The soluble apolipoproteins have very similar genomic structures, each having a total of three introns at the same locations; apoA-IV is an exception in that it has lost its first intron. Using the exon/intron junctions as reference points, we can obtain an alignment of the coding regions of all the soluble apolipoprotein genes. The mature peptide regions of the genes are almost completely made up of tandem repeats of 11 codons. The part of mature peptide region encoded by exon 3 contains a common block of 33 codons, whereas the part encoded by exon 4 contains a much more variable number of internal repeats of 11 codons. On the basis of the degree of homology of the various sequences, and the pattern of the internal repeats in these genes, an evolutionary tree has been proposed for the soluble apolipoprotein genes. ApoB-100 differs considerably from the soluble apolipoproteins. It is the largest apolipoprotein containing 4536 amino acid residues. Two types of internal repeats are identified in apoB-100: amphipathic α-helical repeats and proline-containing repeats with high β-sheet content. The apoB gene contains 29 exons and 28 introns. Its evolutionary relationship to the soluble apolipoprotein genes is unclear. The 3′ end of the apoB gene contains a region of variable number of tandem 12–16-base pair repeats. We have applied the polymerase chain reaction technique to characterize this highly polymorphic locus. The same technique can be used to accurately type other variable number of tandem repeats loci. Finally, apoB-48 was shown to be the product of an RNA editing mechanism involving an intestinal mRNA that has an in-frame UAA stop codon resulting from a C→U change in the codon CAA encoding Gln-2153 in apoB-100 mRNA. Using a molecular approach to apolipoprotein synthesis, structure and genetic analysis, we have generated information important to our understanding of lipoprotein metabolism; we also uncovered unexpected experimental results that are relevant to general cell and molecular biology and molecular evolution.
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  • 40
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    European archives of psychiatry and clinical neuroscience 239 (1989), S. 43-48 
    ISSN: 1433-8491
    Keywords: Schizophrenia ; Eye movements ; Genetics ; Twins ; Latent trait
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Eye movement dysfunctions have been found in a large number of schizophrenic patients and in about half of their first-degree relatives. The distribution of these traits within the families of schizophrenic patients suggests a model of genetic transmission that fits an autosomal dominant model, which we have called the “genetic latent trait model.” The model, with seven parameters, was fitted to a U.S. population and the model was cross-validated on an independent Norwegian sample. Although the model does not invalidate other, more conventional solutions to the puzzle of schizophrenic transmission, such as multifactorial transmission, the latent trait model does more easily permit linkage studies and therefore will allow refutation or support from the use of molecular genetics techniques.
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  • 41
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    Cell & tissue research 255 (1989), S. 385-391 
    ISSN: 1432-0878
    Keywords: Myogenesis ; Muscle regeneration ; Genetics ; Autoradiography ; Tritiated thymidine ; Mouse (Swiss;BALBc)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary Muscle precursor replication in Swiss mice, in which muscle regeneration is exceptionally vigorous, was compared with previous data for regeneration in BALBc mice. The tibialis anterior muscles of 23 male and 15 female inbred Swiss SJL/J mice were crush injured, and tritiated thymidine injected into mice at various times after injury to label replicating muscle precursors. Lesion samples were taken 10 days after injury, processed for autoradiography, and grain counts of myotube nuclei analysed. Muscle regeneration was more vigorous in male compared with female Swiss mice, and in both was strikingly greater than that in BALBc mice in which there was extensive fibrous connective tissue throughout the lesions. Autoradiographic analysis showed that muscle precursor replication started at 24 hours in Swiss mice, 6 hours earlier than the onset at 30 hours in BALBc mice. Muscle precursor replication appeared to be more active 96 hours after injury in female Swiss compared with male BALBc and male Swiss mice respectively, although numbers of precursor cells replicating at other times were similar. It is not known whether the slight difference in onset of muscle precursor replication can alone account for the more complete muscle regeneration seen in Swiss mice. Similar studies were carried out in 11 male and 10 female F1 hybrid (SJL/J x BALBc) mice. Analysis of labelled myotube nuclei showed that muscle precursors did not synthesise DNA prior to 30 hours after injury, and regeneration resembled that of the parental BALBc strain.
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  • 42
    ISSN: 1617-4623
    Keywords: Aspergillus ; Genetics ; Transformation ; trpC lacZ gene fusion ; Gene replacement
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Aspergillus niger tryptophan auxotrophic mutants have been isolated after UV irradiation of conidiospores. The mutants belong to two different complementation groups, trpA and trpB, which complement each other in heterokaryons. Neither of the mutations could be complemented with the cloned A. niger trpC gene. To obtain A. niger trpC mutants in a direct way, gene inactivation by cotransformation was performed. For this purpose an in-frame gene fusion between the A. niger trpC and Escherichia coli lacZ genes was constructed and shown to be functionally expressed after introduction into A. niger by cotransformation with the pyrA gene as selective marker. Among the β-galactosidase expressing cotransformants, obtained with either circular or linearized vectors, no trpC mutants were detected, even after enrichment. Such mutants, however, could be obtained by cotransformation of A. niger with specific fragments of the fusion gene. Biochemical analysis of the cotransformants indicated that in nearly all cases the fusion gene had replaced the wild-type trpC gene. Genetic analysis showed that the trpC mutation is not linked to any of the A. niger loci described so far. The trpC mutants can be complemented by the cloned A. niger trpC gene as well as by the A. nidulans trpC gene.
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  • 43
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 153-157 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Darstellung und röntgenographische Charakterisierung von Doppeloxiden der Formel Cr1-xW1+xO4Mixed-Valenz-Verbindungen der Formel Cr1-xW1+xO4 wurden bei 1300°C dargestellt. Aus Röntgenbeugungsdiagrammen konnten drei verschiedene Phasen identifiziert werden, eine vom Rutiltyp für 0,40 ≤ x ≤ 0,50 und zwei andere mit Rutil-ähnlichen Strukturen bzw. vom CrWO4-Typ für 0 ≤ x ≤ 0,25 und vom WO2-Typ für 0,80 ≤ x ≤ 1.
    Notes: Mixed valency compounds of formula Cr1-xW1+xO4 have been prepared at 1300°C. Three phases have been identified by X-ray diffraction: one of rutile type for 0.40 ≤ x ≤ 0.50 and two others with rutile-related structures, i. e. of CrWO4-type for 0 ≤ x ≤ 0.25 and of WO2-type for 0.80 ≤ x ≤ 1.
    Additional Material: 3 Ill.
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  • 44
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 158-168 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dihalogen(Pentafluorophenyl)sulfonium(IV) Hexafluoroarsenate C6F5SX2+AsF6- (X = Cl, Br) and Crystal Structure of Di(pentafluorophenyl)sulfane (C6F5)2SThe preparation and spectroscopic characterisation of the halogensulfonium salts C6F5SCl2+AsF6- and C6F5SBr2+AsF6- is reported. The new salts are much more stable than their trifluoromethyl derivatives.In addition the crystal structure of (C6F5)2S is reported. Space group P43212, Z = 4, 478 unique observed diffractometer data, Rint. = 0.07, lattice constants: a = 569.0(5) pm, c = 3785.8(22) pm, V = 1225 times; 10-30 m3.
    Notes: Es wird über die Darstellung und spektroskopische Untersuchung der Sulfoniumsalze C6F5SCl2+AsF6- und C6F5SBr2+AsF6- berichtet. Die neuen Salze sind bedeutend stabiler als ihre Trifluormethyl-Homologen.Ergänzend wird die Kristallstruktur von (C6F5)2S mitgeteilt. Raumgruppe P43212, Z = 4, 478 unabhängige Reflexe, Rint. = 0,07, Gitterkonstanten: a = 569,0(5) pm, c = 3785,8(22) pm, V = 1225×10-30 m3.
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  • 45
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 192-192 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 169-176 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Komplexe Kupfer(II)-fluoride. X. Das ternäre System BaF2—CuF2—InF3Das flüssig-fest-Gleichgewichtsdiagramm des InF3—BaF2-Systems wird mittels DTA bestimmt. Die Fluoride BaInF5, das dimorphe Ba3In2F12 und auch eine kubische Phase Ba1-xInxF2+x, deren Struktur sich von der des BaF2 ableitet, wurden gefunden. Die zwei Formen des Ba3In2F12 geben feste Lösungen. Ein isothermer Ausschnitt des ternären Systems BaF2—CuF2—InF3 bei 540°C wird angegeben. Er zeigt die Existenz nur eines quaternären Fluorides: tetragonales BaCuInF7.
    Notes: The liquid-solid equilibria diagram of the InF3—BaF2 system is established by D.T.A. The fluorides BaInF5, the dimorphic Ba3In2F12, and also a cubic phase Ba1-xInxF2+x, the structure of which derives from that of BaF2, are disclosed. The two forms of Ba3In2F12 give solid solutions. An isothermal section of the ternary system BaF2—CuF2—InF3 at 540°C is given. It shows the existence of only one quaternary fluoride: tetragonal BaCuInF7.
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  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 192-192 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 48
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of N-substituted Metal Amides. XIX. Reaction of [Co(NPh2)2]2 with CO - a New Way for the Synthesis of an Chelate Complex of Cobalt (II) with an Derivative of Anthranilic Acid; Molecular Structure of [Co(NPh(o—C6H4CONPh2))2]Reaction of CO (1 atm, room temperature) with [Co(NPh2)2]2 (I) in benzene (mole ratio 3 : 1) gives Co(CO)3(NPh2)4(benzene)1·6 (II). By adding more CO to the reaction mixture (mole ratio 6 : 1) Co4(CO)12 (III) and a dark red compound of the analytical composition C50H38CoN4O2 (IV) could be isolated. The structure of the red compound was determined by X-ray diffraction. This investigation show IV to be a cobalt(II) complex of an derivative of the anthranilic acid, [Co(NPh(o—C6H4CONPh2))2] (IV). The cobalt coordination in this compound is a distorted tetrahedron. Crystal data of IV: space group P1 with a = 12.449(1) Å, b = 12.431(1) Å, c = 13.223(1) Å, α = 95.47(1)°, β = 95.37(1)°, γ = 94.10(1)°, and Z = 2.
    Notes: Bei der Umsetzung von CO (1 atm, Raumtemperatur) mit [Co(NPh2)2]2 (I) in Benzen im Molverhältnis 3 : 1 entsteht Co2(CO)3(NPh2)4(benzen)1,6 (II); im Molverhältnis 6 : 1 bildet sich ein Reaktionsgemisch, aus dem Co4(CO)12 (III) sowie eine dunkelrote Verbindung der analytischen Zusammensetzung C50H38CoN4O2 (IV) isoliert werden kann. Die Röntgenstruktur-bestimmung von IV ergab, daß es sich um den ein Anthranilsäurederivat als Liganden enthaltenden Komplex [Co(NPh(o—C6H4CONPh2))2] IV handelt, der eine verzerrt tetraedrische Koordination aufweist.Kristalldaten für IV: Raumgruppe P1 mit a = 12,449(1) Å, b = 12,431(1) Å, c = 13,223(1) Å, α = 95,47(1)°, β = 95,37(1)°, γ = 94,10(1)° und Z = 2.
    Additional Material: 4 Ill.
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  • 49
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 177-182 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Bildung und Umwandlung von festen Lösungen des δ-Nb2O5 im Nb2O5—Al2O3-SystemIm System Nb2O5—Al2O3 werden (bis 50 Mol-% Al2O3) mit metastabilem, hexagonalem δ-Nb2O5 feste Lösungen gebildet, bei der Präparation aus den amorphen Substanzen, die durch simultane Hydrolyse von Niob- und Aluminiumalkoxid erhalten werden. Die Werte des Gitterparameters a sind unabhängig von der Zusammensetzung, während der Parameter c linear abnimmt mit steigendem Al2O3-Gehalt. Der übergang δ-Nb2O5 (orthorhombisch) erfolgt bei 640°C bis 700°C. Die 50 Mol-% Al2O3-enthaltende feste Lösung geht bei 800° bis 860°C in monoklines NbAlO4 über.
    Notes: In the system Nb2O5—Al2O3, solid solutions of metastable δ-Nb2O5 (hexagonal) are formed up to 50 mol% Al2O3 from amorphous materials prepared by the simultaneous hydrolysis of niobium and aluminium alkoxides. The values of the lattice parameter a are relatively constant regardless of composition, while parameter c decreases linearly with increasing Al2O3 content. The δ- to γ-Nb2O5 (orthorhombic) transformation occurs at ≍ 640°C to ≍ 700°C. The solid solution containing 50 mol% Al2O3 transforms to monoclinic NbAlO4 at 800° to 860°C.
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 570 (1989) 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 51
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 570 (1989), S. 37-53 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of tert.Butyl-lithium with Aluminiumtribromide; Molecular Structures of [HAl(CMe3)2]3 and [LiHAl(CMe3)3]2The reaction of tert.butyl-lithium with aluminiumtrihalide at low temperatures was reinvestigated. Four compounds were isolated: trimeric di(tert.butyl)alane(III) 1, monomeric (solution in benzene)/dimeric (solid state) lithium-tri(tert.butyl)alanate(III) 2, tri(tert.butyl)alane 3 and lithium-tetra(tert.butyl)alanate 4. X-ray structure analyses gave a planar sixmembered Al—H heterocycle for 1 and a Li—H-bridged dimer showing intramolecular interactions of lithium with C—H σ-bonds for 2.
    Notes: Die Reaktion des tert.Butyl-lithiums mit Aluminiumtrihalogenid bei tiefen Temperaturen wurde neu untersucht. Dabei isolierten wir: das trimere Di(tert.butyl)alan(III) 1, das monomere (benzolische Lösung)/dimere (Festkörper) Lithium-tri(tert.butyl)alanat(III) 2 sowie Tri(tert.butyl)alan 3 und Lithium-tetra(tert.butyl)alanat 4. Die Röntgenstrukturanalyse ergab einen planaren sechsgliedrigen Heterozyklus aus Al—H-Einheiten für 1 und ein über Li—H-Brücken verknüpftes Dimeres mit intramolekularen Wechselwirkungen zwischen den Lithiumatomen und C—H-σ-Bindungen für 2.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 106-110 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Ammonium Pentanitrato Praseodymate and Neodymate(NH4)2[Pr(NO3)5] · 4 H2O (I) and (NH4)2[Nd(NO3)5] · 4 H2O (II) were obtained from Pr6O11 and Nd2O3 by reaction with nitric acid and NH4NO3. The fixed water molecules could be removed completely with formation of [NH4]2[Pr(NO3)5] (III) and [NH4]2[Nd(NO3)5] (IV). The i.r. spectra indicate only symmetrically bonded bidentate NO3- ligands. The water molecules are bonded as well by hydrogen bridges to NH4+ ions as by EDA interaction to the lanthanoid atoms. Therefore, the constitution of the complexes is described more exactly by the formula [NH4]2[Ln(NO3)5(H2O)2] · 2 H2O.
    Notes: (NH4)2[Pr(NO3)5] · 4 H2O (I) und (NH4)2[Nd(NO3)5] · 4 H2O (II) lassen sich durch Umsetzung von Pr6O11 bzw. Nd2O3 mit Salpetersäure und Ammoniumnitrat erhalten. Beide Komplexe ließen sich vollständig dehydratisieren unter Bildung von [NH4]2[Pr(NO3)5] (III) bzw. [NH4]2[Nd(NO3)5] (IV). Die Auswertung der IR-Spektren zeigt, daß in den Komplexen ausschließlich zweizähnig gebundene Nitratliganden vorliegen. I und II enthalten unterschiedlich gebundene Wassermoleküle, die teils über Wasserstoffbrücken an die NH4-Ionen, teils koordinativ an die Lanthanoidatome gebunden sind. Die Konstitution dieser Komplexe wird deshalb exakter durch die Formel [NH4]2[Ln(NO3)5(H2O)2] · 2 H2O beschrieben.
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  • 53
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of N-Chloroacetoneimine with Molybdenum Pentachloride and Tungsten Hexachloride. Crystal Structure of Me2C=NH2[MoOCl4]WCl6 reacts with N-chloroacetoneimine under elimination of chlorine and formation of pentachloro-isopropylideneimino-tungsten(VI), Cl5W=N=CMe2, a brown-black crystal powder, which was characterized by i.r. spectroscopy. MoCl5 reacts in a similar way, although only a product mixture can be obtained. Partial hydrolysis of this mixture yields isopropylideneiminium-tetrachlorooxomolybdate(V), Me2C=NH2+[MoOCl4]-, of which the crystal structure was determined (2323 unique observed reflexions, R = 0.049). Space group P21/c, Z = 4, a = 878.6, b = 907.2, c = 1252.2 pm, β = 91.29°. The compound consists of Me2C=NH2+ ions with a planar arrangement of the skeletal atoms and a CN bond length of 126.7 pm and of dimeric, centrosymmetric anions [MoOCl4]22- having Mo atoms linked via asymmetric chloro bridges (MoCl distances 238.4 and 307.6 pm). The longer Mo—Cl contacts are located in the trans-positions of the terminal oxoligands (MoO distance 164 pm).
    Notes: WCl6 reagiert mit N-chloracetonimin unter Chlorabspaltung und Bildung von Pentachlor(isopropylidenimido)wolfram(VI), Cl5W=N=CMe2, einem schwarzbraunen Kristallpulver, das durch sein IR-Spektrum charakterisiert wird. ähnlich verläuft die Umsetzung mit MoCl5, wobei allerdings kein einheitliches Produkt isoliert werden kann. Durch partielle Hydrolyse entsteht aus diesen Produkten Isopropylideniminiumtetrachloro-oxomolybdat(V), Me2C=NH2+[MoOCl4], von dem wir eine Kristallstrukturanalyse angefertigt haben (2323 unabhängige beobachtete Reflexe, R = 4,9%). Raumgruppe P21/c, Z = 4, Gitterabmessungen: a = 878,6; b = 907,2; c = 1252,2 pm; β = 91,29°. Die Verbindung besteht aus Kationen Me2C=NH2+, deren Gerüstatome in einer Ebene liegen und die eine CN-Bindungslänge von 126,7 pm haben, sowie zentrosymmetrischen dimeren Anionen [MoOCl4]22-, deren Mo-Atome über asymmetrische Chlorobrücken mit Mo—Cl-Abständen von 238,4 pm und 307,6 pm verknüpft sind. Die langen Mo—Cl-Kontakte befinden sich in trans-Stellung zu den terminal gebundenen Oxoliganden (Abstand MoO = 164 pm).
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  • 54
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 117-130 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemical Bonding in Crystalline Phases of Cesium Hydrogensulfides, CsHS and CsDSReaction of liquid hydrogensulfide, H2S and D2S respectively, with cesium at room temperature in pressure resistant glass tubes quickly gives the crystalline hydrosulfides, CsHS and CsDS. The compounds are characterized by thermochemical, X-ray, and neutron diffraction data.Three solid phases of CsDS are observed as a function of temperature: Changes in chemical bonding are discussed with respect to temperature and in comparison with alkali metal hydroxides, amides, halides, and further hydrogensulfides.
    Notes: Flüssiger Schwefelwasserstoff, H2S bzw. D2S, reagiert bei Raumtemperatur in druckfesten Glasgefäßen schnell mit Caesium, wobei kristallines Caesiumhydrogensulfid, CsHS bzw. CsDS entsteht. Thermochemische, Röntgen- und Neutronenbeugungsdaten charakterisieren die Verbindungen. Drei feste Phasen von CsDS wurden in Abhängigkeit von der Temperatur beobachtet: Änderungen der chemischen Bindung werden in Abhängigkeit von der Temperatur und durch Vergleich mit Alkalimetallhydroxiden, -amiden und -halogeniden sowie weiteren -hydrogensulfiden diskutiert.
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  • 55
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 111-116 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Crystal Structure of Lithiumhydrogensulfide, LiHSLithiumhydrogensulfide, LiHS, is prepared from lithiumamide, LiNH2, by reaction with liquid hydrogensulfide. At 150°C the solubility of LiHS in H2S is sufficient for the growth of single crystals in a temperature gradient within the autoclaves used. The X-ray structure determination at 295 K is characterized by the following data: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{{{\rm P4}_{\rm 2} } \mathord{\left/ {\vphantom {{{\rm P4}_{\rm 2} } {{\rm mmc,\;Z = 2,\;a = 3.916}\left({\rm 2} \right){\AA},\;c = 6.155\left(2 \right){\AA},}}} \right. \kern-\nulldelimiterspace} {{\rm mmc,\;Z = 2,\;a = 3.916}\left({\rm 2} \right){\AA},\;c = 6.155\left(2 \right){\AA},}}} \hfill \\ {{\rm Z}\left({{\rm F}_{\rm 0}^{\rm 2} \ge 3\sigma \;{\rm F}_{\rm 0}^{\rm 2} } \right) = 74,\;{\rm R = 0.011}{\rm .}} \hfill \\\end{array} $$\end{document} Lithium occupies tetrahedral sites in a distorted cubic close-packed arrangement of S; in PtS sulfur occupies tetrahedral sites in a similar way in a distorted close packing of Pt. Hydrogen atoms of the HS--ions are dynamically disordered in a split position linearly bound to S. At 228 K a thermal effect occurs in DSC-measurements indicating that below this temperature the HS--ion has fixed positions.
    Notes: Zur Darstellung von Lithiumhydrogensulfid, LiHS, wurde Lithiumamid, LiNH2, in flüssigem Schwefelwasserstoff protolysiert. Bei 150°C reicht die Löslichkeit von LiHS in H2S für die Einkristallzüchtung im Temperaturgefälle von Autoklaven aus. Die röntgenographische Strukturbestimmung bei 295 K ist durch folgende Daten charakterisiert: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{{{\rm P4}_{\rm 2} } \mathord{\left/ {\vphantom {{{\rm P4}_{\rm 2} } {{\rm mmc,\;Z = 2,\;a = 3,916}\left({\rm 2} \right){\AA},\;c = 6,155\left(2 \right){\AA},}}} \right. \kern-\nulldelimiterspace} {{\rm mmc,\;Z = 2,\;a = 3,916}\left({\rm 2} \right){\AA},\;c = 6,155\left(2 \right){\AA},}}} \hfill \\ {{\rm Z}\left({{\rm F}_{\rm 0}^{\rm 2} \ge 3\sigma\; {\rm F}_{\rm 0}^{\rm 2} } \right) = 74,\;{\rm R = 0,011}{\rm .}} \hfill \\\end{array} $$\end{document} In einer verzerrt kubisch flächenzentrierten Anordnung von S besetzt Li Tetraederlücken wie S in der ähnlich verzerrten Kugelpackung von Pt in PtS. Die Hydrogenatome der HS--Ionen sind in zwei linear über S verbundenen Positionen dynamisch fehlgeordnet. DSC-Messungen zeigen bei 228 K einen thermischen Effekt, der die Lagefixierung des HS--Ions vermuten läßt.
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  • 56
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 131-136 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Quantum Chemical Model Calculations on the Migration of Si—F Groups in HexafluorosilicatesThe transport of different Si—F species was simulated using two [SiF6]2- octahedra as example. Activation barriers and charge distributions were calculated with the EHT method.Bearing in mind the structure of cubic hexafluorosilicates calculations were carried out on the migration both along an edge and along a (110) face of the elementary cell. At first [SiF2]2+ and SiF4 groups were removed from an [Si2F12]4- unit to produce a surface vacancy. During a second step planar SiF4 groups were moved to the neighbouring lattice position.A diffusion of planar SiF4 is favoured, if the electrostatic interaction between moved and fixed fluorine atoms is as small as possible.
    Notes: Das EHT-Verfahren wurde genutzt, um am Beispiel von zwei [Sif6]2--Baueinheiten den Transport verschiedener SiF-Spezies zu simulieren und dabei die auftretenden Aktivierungsbarrieren und Ladungsverteilungen zu berechnen. Ausgehend von der Struktur kubischer Alkalihexafluorosilicate wurden Rechnungen zum Transport entlang der Kante und entlang einer (110)-Fläche der Elementarzelle durchgeführt. Dabei wurden zunächst [SiF2]2+- bzw. SiF4-Gruppen aus dem [Si2F12]4--Verband zur Schaffung eines freien Oberflächenplatzes entfernt. In einem zweiten Schritt wurden im Modell [SiF8]4- planare SiF4-Gruppen zum jeweils benachbarten Gitterplatz transportiert.Der Transport eines [SiF2]2+-Moleküls erfordert einen wesentlich höheren Energieaufwand als der Transport von planarem SiF4. Eine Diffusion von planarem SiF4 wird begünstigt, wenn eine möglichst geringe elektrostatische Wechselwirkung zwischen den bewegten und feststehenden Fluoratomen stattfindet.
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  • 57
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 145-152 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Structure and Properties of Quaternary Chalcogenides MIAIIIBIVX4VI. III. On the Compounds AgTiZrTe4 and Ag2TiZrTe4Preparation and properties of the compounds AgTiZrTe4 and Ag2TiZrTe4 are reported. The structure deduced from X-ray diffraction diagrams is closely related to the structure of TiZrTe4 showing an ordered accomodation of Ti and Zr atoms at the octahedral sites of the CdI2 type structure. The interlayers free of Ti and Zr atoms are suggested to be in part occupied by Ag+ ions in an ordered sequency, which allows to explain the occurrence of 8 Te layers in the repeating unit.
    Notes: Es wird über die Darstellung der Verbindungen AgTiZrTe4 und Ag2TiZrTe4 und deren Eigenschaften berichtet. Röntgenpulverdiffraktogramme lassen auf enge strukturchemische Beziehungen zum TiZrTe4 mit geordneter Verteilung der Ti- und Zr-Atome auf den Oktaederplätzen des CdI2-Strukturtyps schließen. Für die Ag+-Ionen wird eine partielle Besetzung der Tetraederlücken in den von Ti- bzw. Zr-Atomen freien Zwischenschichten in geordneter Abfolge in Betracht gezogen, die das Auftreten von 8 Te-Schichten in der Wiederholungseinheit erklärt.
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  • 58
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 569 (1989), S. 137-144 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Chalcogenolates. 191. Esters of 2-Oxophenyldithioacetic Acid. 2. Crystal and Molecular Structure of the Methyl EsterThe title compound C6H5—CO—CS—SCH3 crystallizes with Z = 2 in the triclinic space group P1 with cell dimensions (-60°C) a = 6.236(4) Å, b = 7.972(2) Å, c = 9.589(4) Å, α = 88.42(3)°, β = 75.39(5)°, γ = 81.54(4)°. The structure has been determined from single crystal X-ray data measured at -60°C and refined to R = 0.085 and Rw = 0.087 for 2307 independent reflections. With nearly 20° the C=O bond is turned out of the plane of the phenyl ring.
    Notes: Die Titelverbindung C6H5—CO—CS—SCH3 kristallisiert triklin mit Z = 2 in der Raumgruppe P1 mit den Gitterdimensionen (-60°C) a = 6,236(4) Å, b = 7,972(2) Å, c = 9,589(4) Å, α = 88,42(3)°, β = 75,39(5)°, γ = 81,54(4)°. Die Kristallstruktur wurde aus bei -60°C vermessenen röntgenographischen Einkristalldaten unter Verwendung von 2307 symmetrieunabhängigen Reflexen bestimmt und bis auf Zuverlässigkeitsfaktoren von R = 0,085 und Rw = 0,087 verfeinert. Im Molekül ist die C=O-Bindung etwa 20° aus der Ebene des Phenylrings herausgedreht.
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  • 59
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 570 (1989), S. 138-144 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Darstellung und Kristallstruktur eines Cadmiumcyclohexaphosphates: Cd3P6O18 · 6 H2OEs werden die Darstellung und die Kristallstruktur von Cd3P6O18 · 6 H2O beschrieben. Die Verbindung besitzt trigonale (rhomboedrische) Symmetrie, die Elementarzellendaten sind: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm a}_{\rm H} = 15.056(10)} & {{\rm c}_{\rm H} = 16.080(10){\rm }{\AA}} \\ \end{array} $$\end{document} oder \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm a}_{\rm R} = 10.212(10){\rm }{\AA}} & {{\rm \alpha }_{\rm R} = 94.98}\deg \\ \end{array} $$\end{document}Die Raumgruppe ist R3 mit Z = 6 in der hexagonalen Aufstellung. Die Kristallstruktur wurde mit Hilfe von 1355 unabhängigen Reflexen bis zu einem R-Wert von 0,013 bestimmt. Die P6O18-Ringanionen weisen eine dreizähnige Symmetrie auf. Das Cadmium-Koordinationspolyeder ist ein leicht verzerrtes Oktaeder, das von vier Sauerstoff-Atomen und zwei Wassermolekülen gebildet wird. Die Wassermoleküle verknüpfen diese Oktaeder zu Sechsringen mit der Symmetrie 3, diese Ringe wechseln sich entlang der 3-Achse mit den P6O18-Ring-Anionen ab.
    Notes: Chemical preparation and crystal structure of Cd3P6O18 · 6 H2O are described. This compound is trigonal (rhomboedral) with the following unit-cell dimensions: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm a}_{\rm h} = 15.056(10)} & {{\rm c}_{\rm h} = 16.080(10){\rm }{\AA}} \\ \end{array} $$\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm a}_{\rm r} = 10.212(10){\rm }{\AA}} & {{\rm \alpha }_{\rm r} = 94.98}\deg \\ \end{array} $$\end{document}The space group is R3 with Z = 6 for the hexagonal description. The crystal structure has been solved by using 1355 unique reflexions with a final R value 0.013.The P6O18 ring anions have a threefold symmetry. The cadmium coordination polyhedron is a slightly distorted octahedron built up by four oxygen atoms and two water molecules. The water molecules link themselves as to build six-member rings having a 3 symmetry alterning with the P6O18 phosphoric rings along the 3 axes.
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  • 60
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 570 (1989), S. 167-176 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Übergangsmetall-Komplexe mit Thiosemicarbazid-Liganden. VI. Komplexe von NiII und ZnII mit S-AlkylisothiosemicarbazidDurch Umsetzung der ethanolischen Lösung von Ni(OAc)2 · 4 H2O mit S-Alkylisothiosemicarbazid-Iodwasserstoff (L—R · HI; R = Me, Et, n-Pr, n-Bu) und Pyridin wurden die oktaedrischen Bisligand-Komplexe der allgemeinen Formel [Ni(L—R)2Py2]I2 erhalten. Durch Erhitzen bei 95°C bzw. 110°C wurden die Komplexe in die quadratisch-planaren [Ni(L—R)2]I2 (R = Me, Et) - und [Ni(L—R)2I2] (R = n-Pr, n-Bu) - Komplexe mit verzerrt-oktaedrischer Konfiguration überführt. Ferner wurde in ethanolischer Lösung Zn(L—Me)2I2 dargestellt. Die Verbindungen wurden durch Elementaranalyse, TG, magnetische und spektroskopische Messungen charakterisiert.
    Notes: The reaction of warm ethanolic solution of Ni(OAc)2 · 4 H2O with S-alkylisothiosemicarbazide-hydrogeniodide (L—R · HI; R = Me, Et, n-Pr, n-Bu) and pyridine yielded the octahedral bis(ligand) complexes of the general formula [Ni(L—R)2Py2]I2. By the isothermal heating at 95 and 110°C, these complexes were transformed into the square-planar [Ni(L—R)2]I2 (R = Me, Et) complexes and the [Ni(L—R)2I2] (R = n-Pr, n-Bu) complexes of distorted octahedral configuration. Besides, the Zn(L—Me)2I2 complex was prepared. The compounds have been characterized by elemental analysis, magnetic measurements, diffuse reflectance spectra and TG analysis.
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  • 61
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 570 (1989), S. 184-192 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Struktur der geschmolzenen Systeme KF—K2TiF6 und KCl—K2TiF6Die kongruent schmelzenden Verbindungen K3TiF7 und K3TiF6Cl, die in den Systemen KF—K2TiF6 bzw. KCl—K2TiF6 gebildet werden, zeigen einen starken Einfluß auf die Struktur (ionische Zusammensetzung) der Schmelzen der entsprechenden Systeme. In Anbetracht der relativ niedrigen Symmetrie und des hohen Energiezustandes der TiF73-- und TiF6Cl3--Ionen, sollte für sie ein hoher thermischer Dissoziationsgrad erwartet werden. Diese Annahme wird durch zwei verschiedene Methoden - die thermodynamische Analyse der Phasengleichgewichte und der Volumeneigenschaften bestätigt. Die Werte der Schmelzenthalpie für K2TiF6, K3TiF7 und K3TiF6Cl, die zu den Berechnungen verwendet werden, wurden ebenfalls bestimmt.
    Notes: Congruently melting compounds K3TiF7 and K3TiF6Cl which are formed in the systems KF—K2TiF6 and KCl—K2TiF6, respectively, exhibit a strong influence on the structure (ionic composition) of the melts of the corresponding systems. Considering the relatively low symmetry and a high energetic state of the TiF73- and TiF6Cl3- complex ions, a high degree of their thermal dissociation might be expected. This assumption was confirmed by two different methods based on a thermodynamic analysis of the phase equilibria and of the volume properties of the investigated systems, respectively. In connection with the former method, the values of the enthalpy of fusion of K2TiF6, K3TiF7, and K3TiF6Cl which were used in the calculations have also been estimated.
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  • 62
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 568 (1989), S. 22-28 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Experiments about the Mixed Crystal Formation between Zincoxotantalates and -antimonates: ZnTa2-xSbxO6 and Zn4Ta2-xSbxO9In the area of substituted oxotantalates of zinc two new phases of the composition A: ZnTa1·8Sb0·2O6 and B: Zn4Ta1·2Sb0·8O9 were prepared and investigated by X-ray single crystal technique. A crystallizes with tetragonal symmetry (space group D4h14-P42/mnm, a = 4.7314; c = 9.2160 Å; Z = 2). B is monoclinic (space group C2h6-C2/c; a = 15.103; b = 8.839; c = 10.378 Å; β = 93.81°; Z = 8). A crystallizes with trirutile structure, although there is a small replacement of Ta5+ by Sb5+. B maintains the Zn4Ta2O9 structure. One of the point positions of the M5+ ions is occupied statistically by Ta5+/Sb5+ and Zn2+. B is a metastable compound.
    Notes: Im Bereich substituierter Oxotantalate des Zinks wurden zwei neue Phasen A: ZnTa1,8Sb0,2O6 und B: Zn4Ta1,2Sb0,8O9 an Einkristallen röntgenographisch untersucht. A kristallisiert tetragonal (Raumgruppe D4h14-P42/mnm, a = 4,7314; c = 9,2160 Å; Z = 2), B monoklin (Raumgruppe C2h6-C2/c, a = 15,103; b = 8,839; c = 10,378 Å; β = 93,81°; Z = 8). A kristallisiert trotz des geringen Ersatzes von Ta5+ gegen Sb5+ im Trirutiltyp. B behält die Struktur von Zn4Ta2O9 bei. Eine Position der oktaedrisch koordinierten M5+-Ionen ist mit Zn2+ statistisch besetzt. B ist metastabil.
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  • 63
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 573 (1989), S. 143-156 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Oxotungstate with „Channel Structure“: KNa3WO5 (With a Remark on Na4WO5)For the first time single crystals of Na4WO5 were prepared by heating of annealing mixtures of Na2WO4 [2] and Na2O [Na:W = 4,2:1, Ni-cylinder, 725°C, 28 d]. Four-circle-diffraktometer data [PW 1100, 1900 IO(hkl), ω-2Θ scan, AgKα-radiation, R = 6,5%, RW = 5,7%] determine the triclinic structure of Na4WO5 with a = 569.4(2), b = 847.7(2), c = 565.7(1) pm, α = 101.29(2)°, β = 102.25(3)°, γ = 109.20(3)°. It is isotypic with the NaCl-type of structure Li4WO5. By heating Na4WO5 with K2O [Na:K:W = 4:3:1, Au-tube, 750°C, 35 d] colourless single crystals of KNa3WO5 were obtained for the first time. The structure determination [four-circle-diffraktometer data, PW 1100, ω-2Θ scan, 943 IO(hkl), MoKα-Strahlung R = 4.9%, RW = 3.9%] proves space group C2/m with a = 907.8(3), b = 753.9(2), c = 911.8(3) pm, β = 104.07(4)°, Z = 4. The structure is characterised by undulating layers of Na, W and O and two different kinds of channels.The Madelung Part of Lattice Energie, MAPLE, Effective Coordination Numbers, ECON, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.
    Notes: Neu dargestellt wurden farblose Einkristalle von Na4WO5 durch Tempern inniger Gemenge von Na2WO4 [2] und Na2O [Na:W = 4,2:1, Ni-Bömbchen, 725°C, 28 d]. Nach Vierkreisdiffraktometerdaten [PW 1100, 1900 IO(hkl), ω-2Θ-scan, AgKα-Strahlung, R = 6,5%, RW = 5,7%] kristallisiert Na4WO5 triklin mit a = 569,4(2), b = 847,7(2), c = 565,7(1) pm, 101,29(2)°, β = 102,25(3)°, γ = 109,20(3)°, Z = 2. Es ist isotyp mit der Kochsalzvarianten Li4WO5.Durch Erhitzen von Na4WO5 im Gemenge mit K2O [Na:K:W = 4:3:1, Au-Rohr, 750°C, 35 d] wurden erstmals farblose Einkristalle von KNa3WO5 erhalten. Die Strukturaufklärung [Vierkreisdiffraktometerdaten, PW 1100, ω-2Θ-scan, 943 IO(hkl), MoKα-Strahlung R = 4,9%, RW = 3,9%] belegt die Raumgruppe C2/m mit a = 907,8(3), b = 753,9(2), c = 911,8(3) pm, β = 104,07 (4)°, Z = 4. Der Aufbau ist durch gewellte Schichten aus Na, W und O und zwei verschiedene Sorten von Kanälen charakterisiert.Der Madelunganteil der Gitterenergie, MAPLE, Effektive Koordinationszahlen, ECON, diese über Mittlere Fiktive Ionenradien, werden berechnet und diskutiert.
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  • 64
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 573 (1989), S. 185-194 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation of CF3SClF+MF6- (M = As, Sb) and Crystal Structure of CF3SCl2+SbF6-CF3SClF+MF6- (M = As, Sb) is prepared by oxidative fluorination of CF3SCl with XeF+MF6-. The new salt is characterized by IR, Raman and NMR spectra in comparison with CF3SF2+MF6- and CF3SCl2+MF6-. In SO2 solution CF3SClF+SbF6- symmetrizises into CF3SF2+SbF6- and crystalline CF3SCl2+SbF6- with the monoclinic space group P21/c with a = 773.5(14) pm, b = 954.8(15) pm, c = 1242.0(18) pm, β = 100.24(8)°, Z = 4.
    Notes: Die Darstellung von CF3SClF+MF6- (M = As, Sb) erfolgt durch oxidative Fluorierung von CF3SCl mit XeF+MF6-. Das Salz wird schwingungs- und NMR-spektroskopisch charakterisiert, orientierend an den bekannten Daten von CF3SF2+MF6- und CF3SCl2+MF6-. In einer SO2-Lösung symmetrisiert sich CF3SClF+SbF6- zu CF3SF2+SbF6- und einkristallinem CF3SCl2+SbF6- mit der monoklinen Raumgruppe P21/c, a = 773,5(14) pm, b = 954,8(15) pm, c = 1242,0(18) pm, β = 100,24(8)°, Z = 4.
    Additional Material: 4 Ill.
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  • 65
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 568 (1989), S. 136-146 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Rubidium Lithium Zincates: RbLiZnO2 and RbLiZn2O3For the first time colourless single crystals of RbLiZnO2 (A) and RbLiZn2O3 (B) have been prepared. Both crystallize tetragonally, A: space group I4/mmm, Z = 2, a = 351.84(4), c = 1153.3(2) pm; B: space group P42/mnm, Z = 4, a = 1 033.8(1), c = 342.8(1) pm. The crystal structures have been determined from four circle diffractometer data (MoKα; A: 155 hkl, R = 7.9%, Rw = 7.6%; B: 384 hkl, R = 7.0%, Rw = 4.6%). RbLiZnO2 has the BaZn2P2 type of structure while RbLiZn2O3 exhibits a new structure type with linear chains of face shared cubes ∞1[O4/2RbO4/2RbO4/2] as characteristic feature. For both oxides the Madelung part of lattice energy (MAPLE), and effective coordination numbers (ECoN) are calculated.
    Notes: Neu dargestellt wurden die Oxide RbLiZnO2 (A) und RbLiZn2O3 (B) in Form farbloser Einkristalle durch Tempern entsprechender Gemenge der binären Oxide. Beide Zincate kristallisieren tetragonal, A: Raumgr. I4/mmm, Z = 2, a = 351,84(4), c = 1153,3(2) pm; B: Raumgr. P42/mnm, Z = 4, a = 1 033,8(1), c = 342,8(1) pm. Die Kristallstrukturen wurden aus Vierkreisdiffraktometerdaten (MoKα) bestimmt (A: 155 hkl, R = 7,9%, Rw = 7,6%; B: 384 hkl, R = 7,0%, Rw = 4,6%). RbLiZnO2 kristallisiert im BaZn2P2-Strukturtyp, RbLiZn2O3 zeigt eine neue Struktur mit charakteristischen Würfel-Doppelketten ∞1[O4/2RbO4/2RbO4/2]. Der Madelunganteil der Gitterenergie (MAPLE) sowie effektive Koordinationszahlen (ECoN) wurden jeweils berechnet.
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  • 66
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 568 (1989), S. 147-150 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the α-NaFeO2-Type: On KPrO2For the first time we obtained yellow-green single crystals of KPrO2 by annealing K2PrO3 in Ni-cylinders [1 000°C; 4 weeks]. The structure determination confirms the trigonal rhombohedral α-NaFeO2-type: a = 365.11(3), c = 1 859.65(21) pm, c/a = 5.09, Z = 3, spacegroup R3m, fourcircle diffractometer data (Philips PW 1100), MoKα, 134 Io(hkl), R = 2.58%, Rw = 2,42%.
    Notes: Erstmals erhielten wir gelbgrüne Einkristalle von KPrO2 durch Tempern von K2PrO3 in Ni-Bömbchen [1000°C; 4 Wochen]. Es liegt der trigonal-rhomboedrische α-NaFeO2 Typ vor: a = 365,11(3), c = 1 859,65(21) pm, c/a = 5,09, Z = 3, Raumgruppe R3m, Vierkreisdiffraktometerdaten (Philips PW 1100), MoKα, 134 Io(hkl), R = 2,58%, Rw = 2,42%.
    Additional Material: 5 Tab.
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  • 67
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 573 (1989), S. 208-214 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation of Ceramic Powders. II. Mg2TiO4, MgTiO3, and MgTi2O5 Formed by Hydrolysis of 2-EthoxyethylatesSolutions of 2-ethoxyethylates of magnesium and titanium in 2-ethoxyethanol submitted to hydrolysis, evaporation and heating of the residue up to 450°C allow to prepare Mg2TiO4, MgTiO3, and MgTi2O5 in an amorphous state with smaller than 1% of volatile components. Highly dispersed powders showing an increased sintering activity are obtained as a result of recrystallization. Mg2TiO4 is formed as inverse spinel phase in a metastable state.
    Notes: Die 2-Ethoxyethylate von Magnesium und Titan bilden in 2-Ethoxyethanol stabile Lösungen, deren Hydrolyse nach dem Abdestillieren des Lösungsmittels und Erhitzen des Rückstandes bis auf 450°C die Herstellung von Mg2TiO4, MgTiO3 und MgTi2O5 im amorphen Zustand mit weniger als 1% flüchtigen Bestandteilen gestattet. Die Rekristallisation führt zu hochdispersen sinteraktiven Pulvern, im Fall von Mg2TiO4 zur Bildung der inversen Spinellphase unter metastabilen Bedingungen.
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  • 68
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Elektrochemische Synthese von neutralen Nickel(II)-Komplexen mit Schiffschen Basen: Kristallstruktur von Bis-{N-[2-(2-pyridyl) äthyl]-salicylideneiminato}nickel(II) TrihydratNickel(II)-Komplexe mit im Pyridin-Ring substituiertem N-2-(2-pyridyl)-äthyl-salicylideneiminat wurden durch Elektrolyse einer nicht wäßrigen Lösung des entsprechenden Liganden hergestellt; als Anode diente ein Ni-Draht. Die Struktur von Bis-{N-[2-(2-pyridyl)äthyl]-salicylideneiminato}nickel(II). Trihydrat wurde röntgenographisch bestimmt. Der Komplex kristallisiert triklin in der Raumgruppe P1 mit den Gitterkonstanten a = 13,055(4) Å, b = 13,097(6)Å, c = 16,189(5) Å, α = 102,92(3)°, β = 99,80(3)°, γ = 90,42(3)° und Z = 4. Eine Least-squares-Verfeinerung führte zu einem R-Wert von 0,047. Das Molekül ist nicht zentrosymmetrisch, da die zwei dreizähnigen Liganden eine meridionale Konfiguration um das oktaedrisch koordinierte Nickel(II) annehmen.
    Notes: Nickel(II) complexes with N-2-(2-pyridyl)ethyl-ring substituted salicylideneiminatos have been synthesized by an electrochemical procedure using a sacrificial anode in non-aqueous solution of the corresponding ligand. The structure of bis{N-[2-(2-pyridyl)]-salicylideneiminato}-nickel (II) trihydrate has been determined by X-ray diffraction. Crystals are triclinic, space group P1, with four formula units in a cell of dimensions a = 13.055(4) Å, b = 13.097(6) Å, c = 16.189(5) Å, and α = 102.92(3)°, β = 99.80(3)°, γ = 90.42(3)°. Full matrix least squares refinement on R converged with a conventional agreement factor of 0.047. The molecule is non-centrosymmetric with two terdentate ligands in a meridional configuration around octahedral nickel(II).
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  • 69
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 573 (1989), S. 240-240 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 70
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 573 (1989), S. 223-230 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pollucit- und Leucit-verwandte Phasen: A2BX5O12 und ACX2O6 (A = K, Rb, Cs; B = Be, Mg, Fe, Co, Ni, Cu, Zn, Cd; C = B, Al, Ga, Fe, Cr; X = Si, Ge)Darstellung und kristallographische Daten von 29 neuen Phasen dieser Strukturfamilie werden angegeben. Ein Überblick über die gesamte Strukturfamilie, die bis jetzt 59 Phasen enthält, wird gegeben. Die Familie enthält wenigstens sieben Strukturvarianten, von denen zwei die Pollucit-, CsAlSi2O6, und Leucit-, KAlSi2O6, Struktur sind. Beziehungen zwischen der Kationengröße und dem Strukturtyp werden vorgestellt. Ungewöhnliche Variationen in den Größen der Einheitszelle als Funktion der Kationengröße werden diskutiert, und auf die mögliche Bedeutung für das „partially collapsed framework“-Konzept von Taylor und Henderson wird hingewiesen.
    Notes: Synthesis and crystallographic data on 29 new phases in this family are given. A survey of the crystal chemistry of the complete family, containing 59 phases to date, is presented. The family contains at least seven structural variations, two of which are the pollucite, CsAlSi2O6 and leucite, KAlSi2O6 structures. Correlations between cation size and structure type are presented. Unusual variations in unit cell dimensions as a function of cation size are discussed and the possible relevance of the „partially collapsed framework“ concept of Taylor and Henderson indicated.
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  • 71
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 573 (1989), S. 231-239 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies of the Heterogeneous Catalytical Ring Alkylation of Toluene with Methanol on Modified Zeolites ZSM-5Various ways for controlling the catalytic activity, the shape selectivity, and the deactivation behaviour of modified zeolites ZSM-5 has been shown by the example of the heterogeneous catalytical conversion of toluene with methanol. The preferred formation of the industrially interesting para-xylene is possible by use of ZSM-5-zeolites composed of large crystals, by dealumination of the external surface after hydrothermal treatment, by poisoning of external active centres after impregnation with inorganic salts as well as by isomorphic incorporation of boron for silicon and/or aluminium in the zeolite framework.
    Notes: Am Beispiel der heterogen-katalysierten Umsetzung von Toluen mit Methanol wurden verschiedene Wege zur Steuerung der katalytischen Aktivität, der Formselektivität und des Desaktivierungsverhaltens modifizierter H-ZSM-5-Zeolithe aufgezeigt. Eine Ausprägung der bei der Toluenmethylierung technisch interessanten para-Xylen-Selektivität gelingt durch den Einsatz von großkristallinen ZSM-5-Zeolithen, durch Dealuminieren der äußeren Oberfläche mittels hydrothermaler Behandlung, durch Vergiften äußerer aktiver Zentren mittels Tränkung anorganischer Salze sowie durch den isomorphen Einbau von Bor für Silicium und/oder Aluminium im Zeolithgerüst.
    Additional Material: 5 Ill.
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  • 72
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 73
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    Zeitschrift für anorganische Chemie 573 (1989), S. 240-240 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 74
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 575 (1989) 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 75
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 575 (1989), S. 7-9 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 76
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 575 (1989), S. 10-16 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, IR Spectrum, and Crystal Structure of N,N'-Bis(trimethylsilyl)benzamidinium Tetrachloroferrate(III)The title compound [C6H5—C(NHSiMe3)2][FeCl4] is obtained by the reaction of FeCl3 with N,N,N'-tris(trimethylsilyl)benzamidine in the presence of tetrahydrofurane, forming yellow, moisture sensitive crystals. The compound is characterized by its IR spectrum as well as by an X-ray structure determination. Space group P21/n, Z = 8, 5974 independent observed reflexions, R = 0.066. The lattice dimensions are at -70°C: a = 2110.7, b = 1109.5, c = 2120.4 pm; β = 111.17º. The compound forms ion pairs, in which the H atoms of the amidinium cation are coordinated with one chlorine ligand of the FeCl4- ion in a chelating manner.
    Notes: Die Titelverbindung [C6H5—C(NHSiMe3)2][FeCl4] entsteht in Form gelber feuchtigkeitsempfindlicher Kristalle bei der Einwirkung von Eisen(III)chlorid auf N,N,N'-Tris(trimethylsilyl)benzamidin in Gegenwart von Tetrahydrofuran. Die Verbindung wurde durch das IR-Spektrum und durch eine Kristallstrukturanalyse charakterisiert. Raumgruppe P21/n, Z = 8, 5974 unabhängige beobachtete Reflexe, R = 6,6%. Die Gitterkonstanten betragen bei -70°: a = 2110,7; b = 1109,5; c = 2120,4 pm; β = 111,17º. Die Verbindung bildet Ionenpaare, in denen die H-Atome des Amidiniumkations eines der Chloratome des FeCl4--Anions chelatartig umgeben.
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  • 77
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 575 (1989), S. 26-30 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ni5HfB2O10 with Ordered Metal DistributionNi5HfB2O10 was prepared for the first time and investigated by X-ray methods. It crystallizes with orthorhombic symmetry, space group D2h16 - Pnma, a = 9.328; b = 6.120; c = 12.334 Å; Z = 4. In opposition to the Ni5TiB2O10-type all metal point positions are strongly ordered. The authors are in doubt about the partly statistic metal distribution within Ni5M4+B2O10 (M4+ = Ti, Zr, Ge).
    Notes: Ni5HfB2O10 wurde erstmals dargestellt und an Einkristallen untersucht. Ni5HfB2O10 kristallisiert orthorhombisch, Raumgruppe D2h16 - Pnma, a = 9,328; b = 6,120; c = 12,334 Å, Z = 4. Im Gegensatz zum Ni5TiB2O10-Typ weist NiHfB2O10 eine total geordnete Metallverteilung auf. Die partiell statistische Verteilung von Ni2+ mit M4+ (M4+ = Ti, Zr, Ge) wird in Frage gestellt.
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  • 78
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 575 (1989), S. 17-25 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 27Al NMR Studies on Alkali FluoroaluminatesThe 27Al NMR spectra of the alkali fluoroaluminates sensitively reflect the kind of condensation of the AlF6 octahedra. Whereas the chemical shift of the octahedral Al is shown to be rather independent on structural details, clear differences in the electric field gradients of isolated and condensed AlF6 octahedra were found. In contrast to the isolated octahedra which show only weak effects of quadrupole interaction, both for chains and layers of AlF6 octahedra axial EFG tensors result with quadrupolar coupling constants of between 10 and 13 MHz; for the threefold chains in CsAlF4 only a value of 7.5 MHz is obtained.
    Notes: Die 27Al-NMR-Spektren der Alkalifluoroaluminate spiegeln in empfindlicher Weise die Verknüpfung der AlF6-Oktaeder wider. Während sich die chemische Verschiebung für das oktaedrisch koordinierte Aluminium als nahezu unbeeinflußt von strukturellen Details erweist, ergeben sich deutliche Unterschiede in den elektrischen Feldgradienten (EFG) zwischen isolierten und verknüpften AlF6-Oktaedern. Im Gegensatz zu den isolierten Oktaedern, bei denen Quadrupolwechselwirkungseffekte nur eine untergeordnete Rolle spielen, ergeben sich sowohl für Ketten als auch schichtförmige Verknüpfung der AlF6-Oktaeder axiale EFG-Tensoren mit Quadrupolkopplungskonstanten zwischen 10 und 13 MHz, bei Verknüpfung als Dreierstrangkette im CsAlF4 lediglich ein Wert von 7,5 MHz.
    Additional Material: 3 Ill.
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  • 79
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemical, Thermoanalytical, and X-ray Investigations to the Formation of the β-Ca2[P2O7] from the Ca2[P4O12] · 4 H2OThe formation of β-Ca2[P2O7] from Ca2[P4O12] · 4 H2O (modification I) proceeds crystallographically oriented in several steps: In one of these steps an X-ray amorphous phase is formed and simultaneously cyclotetraphosphate reorganizes to polyphosphate. The dehydration proceeds in 2 steps: At 120°C 3 molecules and at 220°C 1 molecule are lost, respectively. The formation of diphosphate from polyphosphate, which is connected with the loss of P2O5, takes place at 850°C according to high temperature Guinier.
    Notes: Die Bildung des β-Ca2[P2O7] aus dem Ca2[P4O12] · 4 H2O (Form I) läuft über mehrere Stufen kristallographisch orientiert ab. Eine der Zwischenstufen ist röntgenamorph. Bei ihrer Bildung entsteht aus dem Cyclotetraphosphat höherkondensiertes Polyphosphat. Die Wasserabgabe erfolgt in zwei Schritten: Bei 120°C werden 3 Mol, bei 220°C ein Mol H2O abgegeben. Der mit P2O5-Abgabe verbundene übergang Poly- in Diphosphat erfolgt laut Heizguinier bei 850°C.
    Additional Material: 2 Ill.
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  • 80
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 572 (1989) 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 81
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 577 (1989), S. 74-82 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organometallic Chemistry with P/N-Chelating Ligands. I. Molybdenum and Iron(0) Compounds of 2-DiphenylphosphinomethylpyridineThe reaction of 2-diphenylphosphinomethylpyridine 1 (PN) with norbornadiene-tetracarbonylmolybdenum gives (PN)Mo(CO)4 2 in good yield. The acetonitrile ligands in (π-C3H5)Mo(CO)2(CH3CN)2Br 3 are easily exchanged by 1. The thus formed complex (π-C3H5)(PN)Mo(CO)2Br 4 undergoes a reductive deallylation with further 1 to afford cis-(PN)2Mo(CO)2 6. Deallylation of 3 by triphenylphosphine and subsequent reaction with 1 yields the complex cis-(CO)2-trans-(PPh3)2Mo(PN) 7. Ligand 1 displays a chelating function in all of the molybdenum complexes. The structures of the (PN)-complexes are deduced mainly from the nmr data. The initial product of the photochemical reaction of 1 with ironpentacarbonyl is (PN)Fe(CO)4 8, followed by trans-(PN)2Fe(CO)3 9. In both cases 1 is bonded via the phosphorus atom only. Prolonged irradiation affords the chelated tricarbonyl (PN)Fe(CO)3 10. The thermal reaction of 1 with Fe2(CO)9 is different in that the first product is a sensitive red compound 11, which still contains bridging carbonyl groups and has to be formulated as (PN)Fe2(CO)7. Longer reaction times, but also the reaction of 8 with Fe2(CO)9 finally give a new type of complex, (PN)Fe2(CO)6 12, without bridging carbonyls.
    Notes: Mit 2-Diphenylphosphinomethylpyridin 1 (PN) wird aus Norbornadien-tetracarbonylmolybdän (PN)Mo(CO)4 2 erhalten. Im π-Allyl-Komplex (π-C3H5)Mo(CO)2(CH3CN)2Br 3 läßt sich das Acetonitril leicht gegen 1 austauschen. Der so gebildete Komplex (ß-C3H5)(PN)Mo(CO)2Br 4 reagiert mit weiterem 1 unter reduktiver Entallylierung zu cis-(PN)2Mo(CO)2 6, während man durch vorangehende Entallylierung von 3 durch Triphenylphosphin und nachfolgende Reaktion mit 1 den Komplex cis-(CO)2-trans-(PPh3)2Mo(PN) 7 erhält. In allen Molybdänkomplexen hat 1 Chelatfunktion. Die Strukturen können für die (PN)-Komplexe insbesondere aus den NMR-Spektren erschlossen werden. Mit Eisenpentacarbonyl wird photochemisch zunächst (PN)Fe(CO)4 8, als nächstes trans-(PN)2Fe(CO)3 9 gebildet. In beiden Fällen ist 1 nur über den Phosphor gebunden. Bei längerer Bestrahlung wird auch das Chelat-tricarbonyl (PN)Fe(CO)3 10 erhalten. Anders verläuft die thermische Reaktion von 1 mit Fe2(CO)9, bei der zunächst ein empfindliches, rotes Produkt 11 gebildet wird, das noch Brückencarbonylgruppen enthält und als (PN)Fe2(CO)7 formuliert werden muß. Längere Reaktionszeiten, aber auch die Reaktion von 8 mit Fe2(CO)9 ergeben schließlich ein neuartiges Produkt (PN)Fe2(CO)6 12 ohne Brückencarbonyl.
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  • 82
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 577 (1989), S. 115-121 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Organometallic Metallacyclic Transition Metal Compounds. I. Synthesis and Properties of Li2(solv)x and its Reaction with CO2The reaction of ZrCl4(thf)2 with LiCH2CH2CH2CH2Li at -78°C in diethyl ether and addition of tetrahydrofuran (thf) yield Li2Zr(C4H8)3(thf)5,5 (I). The displacement of thf by dioxane (dx) or tetramethylethylenediamine (tmed) gives Li2Zr(C4H8)3(dx)3 (Ia) or Li2Zr(C4H8)3(tmed)3 (Ib). I decomposes at room temperature, Ia and Ib however are stable at room temperature for a short time.The reaction between I and CO2 and subsequent treatment of the reaction mixtures with water yield .
    Notes: Die Umsetzung von ZrCl4(thf)2 mit LiCH2CH2CH2CH2Li bei -78°C in Diethylether führt nach Zugabe von Tetrahydrofuran (thf) zur Bildung von Li2Zr(C4H8)3(thf)5,5 (I). Der Austausch von thf gegen 1,4-Dioxan (dx) bzw. Tetramethylethylendiamin (tmed) ergibt die kristallinen Verbindungen Li2Zr(C4H8)3(dx)3 (Ia) bzw. Li2Zr(C4H8)3(tmed)3 (Ib). Während die Zer-setzung von I bei Raumtemperatur sehr bald unter Dunkelfärbung beginnt, sind Ia und Ib begrenzte Zeit bei Raumtemperatur lagerfähig.Die Umsetzung von I mit CO2 und anschließende Hydrolyse der Reaktionsprodukte ergeben .
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  • 83
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 576 (1989), S. 255-266 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Strukture of the First Six-membered Selena- and PlatinatriazaphosphorinesThe reaction of PhCN with Li[N(SiMe3)2], Ph2PCl and Me3SiN3 leads to the starting material (Me3Si)2NC(Ph)NP(Ph)2N(SiMe3) 1. 1-Chloro-3,3,5-triphenyl-1λ4,2,4,6,3λ5-selenatriazaphosphorine 2 is formed when 1 is treated with SeCl4. (Ph3P)2Pt(C2H4) as well as (Ph3P)4Pt react with 1 to yield the six-membered platinum containing heterocycles 2 and 4. The six-membered rings 2 and 4 were characterized by and X-ray single crystal structure analysis.
    Notes: Die Reaktion von PhCN mit Li[N(SiMe3)2], Ph2PCl und Me3SiN3 führt zu der Ausgangsverbindung (Me3Si)2NC(Ph)NP(Ph)2N(SiMe3) 1. Mit SeCl4 und 1 entsteht das 1-Chlor-3,3,5-triphenyl-1λ4,2,4,6,3λ5-selenatriazaphosphorin 2. Sowohl (Ph3P)2Pt(C2H4) als auch (Ph3P)4Pt reagieren mit 1 unter Bildung der sechsgliedrigen, platinhaltigen Heterocyclen 2 und 4. Die sechsgliedrigen Ringe 2 und 4 werden durch eine Einkristall-Röntgenstrukturanalyse charakterisiert.
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  • 84
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation of Cyclophosphates, Cyclophosphatophosphonates, Diphosphonates, and Di-phosphites in Urea MeltsAmmonium cyclotriphosphate (NH4)P3O9, ammonium cyclotetraphosphate [PIV—PIV —O—]2, ammonium cyclotriphosphatophosphonates Ammonium organyldiphosphonates And ammonium diphosphites are prepared in high yields on heating acidic phosphates, phosphonates, and phosphites in urea or urea/ammonium nitrate melts. The mechanism of the dehydration of phosphorus compounds containing POH groups in molten urea is discussed.
    Notes: Durch Erhitzen (140-200°C) von sauren Phosphaten, Phosphonaten und Phosphiten in Harnstoff- oder Harnstoff/Ammoniumnitrat-Schmelzen wurden in hohen Ausbeuten hergestellt: Ammoniumcyclotriphosphat (NH4)3P3O9, Ammoniumcyclotetraphosphat [PIV—PIV—O—]2, Ammoniumcyclotriphosphatophosphonate (Dioxatriphosphinane)Ammoniumorganyldiphosphonate und Ammoniumdiphosphit (NH4)2P2O5.Der Mechanismus der Dehydratisierung von POH-Gruppen enthaltenden Phosphorverbindungen in geschmolzenem Harnstoff wird diskutiert.
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  • 85
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 577 (1989) 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 86
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Oxidation of Formic Acid Catalyzed by Giant Palladium ClustersLiquid-phase oxidation of formic acid by oxygen in acetonitrile solutions is catalyzed by giant clusters Pd561Phen60(OAc)180 or Pd561Phen60(O)60 at 20-70°C. The reaction is first-order in the cluster and formic acid concentrations. Dependence of the reaction rates on O2 concentration is described by Michaelis-type equation. Kinetic isotope effects are found to be k(HCOOH)/k(HCOOD) = 1.1 ± 0.1 and k(HCOOH)/k(DCOOD) = 1.0 ± 0.1. On the base of the kinetic data the reaction mechanism is discussed.
    Notes: Die Flüssigphasenoxydation von Ameisensäure durch molekularen Sauerstoff wird in Acetonitrillösung und Temperaturen von 20 bis 70°C durch die Riesencluster des Palladiums Pd561Phen60(OAc)180 oder Pd561Phen60(O)60(PF)60 katalysiert. Diese Oxydation verläuft als Reaktion erster Ordnung bezüglich der Cluster- und Ameisensäurekonzentration. Eine Beziehung vom Typ der Michaelis-Gleichung beschreibt die Abhängigkeit der Reaktionsgeschwindigkeit von der O2-Konzentration. Die kinetischen Isotopieeffekte betragen: k(HCOOH)/k(HCOOD) = 1,1 ± 0,1 und k(HCOOH)/k(DCOOD) = 1,0 ± 0,1. Auf der Grundlage der kinetischen Daten wird der Reaktionsmechanismus diskutiert.
    Additional Material: 5 Ill.
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  • 87
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 577 (1989), S. 23-38 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Theoretical Investigations on the Charge Transfer of d6-Metal Complexes with Acceptor LigandsOn the basis of the electronic structure of pentaammineruthenium(II) and pentacyanoferrate(II) complexes with aromatic N-heterocyclic ligands L the different tendency of the complex fragments to charge-transfer interactions with acceptor molecules is discussed. The increased energy and the reduced absorption intensity of the metal oxidation band of [Fe(CN)5L]3- are due to the diminished orbital interaction between the pentacyanoferrate(II) fragment and the nitrogen acceptor ligand caused by π-bonding interaction of the central metal with the cyanide co-ligands. The possibility of the variation of the energy of the acceptor levels connected with the position of the MLCT bands of the mixed-ligand complexes has been investigated by numerous azine and α-diimine ligands of different structure. Besides inductive and mesomeric effects the steric influences on the π-acceptor ability of the ligand and on the energy and absorption intensity of the MLCT band are examined.
    Notes: Auf der Grundlage der Elektronenstruktur von Pentamminruthenium(II)-und Pentacyanoferrat(II)-Komplexen mit aromatischen N-heterocyclischen Liganden wird die unterschiedliche Tendenz der Komplexfragmente zur Charge-Transfer-Wechselwirkung mit Akzeptorliganden diskutiert. Die verringerte Orbitalwechselwirkung des Pentacyanoferrat(II)-Fragments mit dem N-Akzeptor ist die Ursache für die höhere Energie und die reduzierte Absorptionsintensität der Metalloxydationsbande. Sie resultiert aus der zusätzlichen π-Bindungswechselwirkung zwischen dem Metallzentrum und den Cyanidliganden. Am Beispiel unterschiedlicher Azin- und α-Diiminliganden werden Möglichkeiten zur Variation der Energie des Akzeptorniveaus und damit der energetischen Position der MLCT-Bande untersucht. Neben induktiven und mesomeren Effekten werden vor allem die sterischen Einflüsse auf die π-Akzeptorfähigkeit des Liganden und ihre Auswirkung auf die Energie und die Absorptionsintensität der MLCT-Bande betrachtet.
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  • 88
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 577 (1989), S. 59-73 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Relative Donor-Acceptor-Properties of Monodentate Ligands. An EHT-StudyThe relative donor-acceptor properties of some important monodentate ligands are investigated by means of the extended Hückel method and a suitable graduation is determined. Charge gradations are discussed and results compared with known facts. Acceptor properties of ligands with phosphorous and sulfur atoms are described in the best manner using charge iterations at the atoms mentioned.
    Notes: Mit Hilfe der EHT-Methode werden die relativen Donor- und Akzeptor-Eigenschaften einiger wichtiger einzähniger Komplexliganden untersucht und eine entsprechende Abstufung ermittelt. Ladungsdifferenzierungen werden diskutiert und die Ergebnisse mit bekannten Erkenntnissen verglichen. Durch die Ladungsiteration an Phosphor- und Schwefelliganden lassen sich die Akzeptoreigenschaften dieser Moleküle relativ gut beschreiben.
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  • 89
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 577 (1989), S. 93-101 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Semiquinone and Catecholate Coordination Compounds of the Late 3d-Metals9,10-Phenanthrenequinone reacts on a different way with olefine complexes of iron, cobalt, and nickel, obtaining semiquinone and catecholate coordination compounds. These compounds are also formed by a reducing process of metal salts and phenanthrenequinone. Some mono- and dimeric semiquinone complexes are prepared by an additional coordination of tetramethyl-ethylenediamine or inner complexes of salene type as chelate ligands. The new chelates are characterized by the magnetic moments, the u.v./vis., the i.r., and the e.s.r. spectra.
    Notes: 9,10-Phenanthrenchinon reagiert auf unterschiedliche Weise mit Olefinkomplexen des Eisens, Cobalts und Nickels, wobei Semichinon- oder Catecholat-Komplexe entstehen. Diese Verbindungen können auch durch reduktive Umsetzung aus den Metallsalzen und Phenanthrenchinon erhalten werden. Zusätzliche Koordination von Tetramethylethylendiamin oder von Salen-Innerkomplexen führt zu einer Reihe von mono- und dinuclearen Semichinon-Komplex-verbindungen. Die Charakterisierung der Produkte erfolgt anhand der magnetischen Momente und mittels IR-, UV/VIS- sowie ESR-Spektroskopie.
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  • 90
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 578 (1989), S. 18-26 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Neutron Diffraction on Li2CuO2Li2CuO2 was investigated by neutron powder diffraction at 300 K and 4.2 K (diffractometer SV7 at FRJ-2 in KFA Jülich, λ = 109 pm).The crystallographic orthorhombique space group Immm determined previously by x-ray diffraction on single crystals was confirmed. Lattice parameters and atomic positional parameters were refined: a = 366.14(8), b = 286.14(6), c = 939.4(2) pm; z(Li) = 0.7122(17), z(O) = 0.6411(7).Li2CuO2 orders antiferromagnetically below 10 K with an antiparallel coupling of the magnetic moments of Cu2+ in (0, 0, 0) and (1/2, 1/2, 1/2). The moments are orientated perpendicular to the c-axis. The ordered magnetic moment is μ = 0.9(1) μB per Cu2+ at 4.2 K. The magnetic Bravais-Lattice is PI, the magnetic space group is PImmm with similar parameters.
    Notes: Li2CuO2 wurde mit Neutronenpulverdiffraktometrie bei 300 K und 4,2 K untersucht (Diffraktometer SV7 am FRJ-2 in KFA Jülich, λ = 109 pm).Die aus Röntgen-Einkristalldaten bestimmte orthorhombische Raumgruppe Immm wurde bestätigt, Gitterkonstanten und Atompositionsparameter wurden verfeinert: a = 366,14(8), b = 286,14(6), c = 939,4(2) pm; z(Li) = 0,7122(17), z(O) = 0,6411(7).Unterhalb von 10K ordnet Li2CuO2 antiferromagnetisch mit einer antiparallelen Einstellung der magnetischen Momente von Cu2+ in (0, 0, 0) und (1/2, 1/2, 1/2). Die Momentorientierung ist senkrecht zur c-Achse. Das geordnete magnetische Moment beträgt μ = 0,9(1) μB pro Cu2+ bei 4,2 K. Das magnetische Bravais-Gitter ist PI, die magnetische Raumgruppe bei gleichen Gitterkonstanten PImmm.
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  • 91
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pseudochalcogen Compounds. XXI. Synthesis of Phosphorus(III) and Phosphorus(V) OrganocyanamidesThe synthesis of a series of phosphorus(III) and phosphorus(V) organocyanamides of the general formulas P(YR)3, P(X)(YR)3, P(X)(OR′)(YR)2, and P(X)(OR′)2(YR) (Y : NCN; X : O, S) by reactions of the corresponding phosphorus and organophosphorus chlorides with metal organocyanamides is reported. The cyanamide structure (P—N(CN)—R) of the new compounds is confirmed by infrared data as well as by a modified synthetic route. A comparison of 31P-NMR data of homologous cyanamide- and oxo-phosphorus derivatives is confirming the pseudochalcogen character of the NCN-group.
    Notes: Es wird über die Synthese einer Reihe von Phosphor(III)- und Phosphor(V)-organocyanamiden der allgemeinen Formeln P(YR)3, P(X)(YR)3, P(X)(OR′)(YR)2 und P(X) (OR′)2(YR)(Y : NCN, X : O, S) durch Reaktionen der entsprechenden Phosphor- und Organophosphorchloride mit Metall-organocyanamiden berichtet. Der in den neuen Verbindungen generell vorliegende Cyanamid-Bindungstyp (P—N(CN)R) folgt aus IR-Daten ebenso wie aus einem modifizierten Syntheseweg. Ein Vergleich der 31P-NMR chemischen Verschiebungen homologer Oxo- und Cyanamido-Phosphor-Derivate bestätigen den Pseudochalkogen-Charakter der NCN-Gruppe.
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  • 92
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 578 (1989), S. 81-88 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Phosphole Complexes of 3d Transition MetalsThe 2-ethoxy-, 2-cyclohexanoxy-, 2-phenoxy-, 2-(4′-methylphenoxy)- and 2-(4′-chlorphenoxy)-benzo[1,3,2]-dioxaphospholcomplexes of chromium(III), iron(II), cobalt(II), and nickel(II) are synthesized and characterized by N.M.R., I.R. and U.V.-VIS spectroscopy and by magnetic investigations. When titanium(IV) ore copper(II) halides are used redox-reactions can be observed. The corresponding copper(I) complexes are isolated.
    Notes: Es werden 2-Ethoxy-, 2-Cyclohexanoxy-, 2-Phenoxy-, 2-(4′-Methylphenoxy)- und 2-(4′-Chlorphenoxy)benzo[1,3,2]dioxaphospholkomplexe des Chrom(III), Eisen(II), Cobalt(II) und Nickel(II) synthetisiert und mittels NMR-, IR- und UV-VIS-Spektroskopie sowie durch magnetische Untersuchungen charakterisiert. Im Falle des Titan(IV) und des Kupfer(II) werden Redoxreaktionen beobachtet, es werden entsprechende Kupfer(I)-Komplexe isoliert und im Falle des 2-(4′-Chlorphenoxy)-benzol[1,3,2]dioxaphospholliganden der Kupfer(II)-Komplex nachgewiesen.
    Additional Material: 2 Ill.
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  • 93
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Complexes with Sulfur Ligands. XLIV. Ruthenium(II) Complexes with the Sterically Demanding Thioether-thiolate Ligand ‚buS4‘2-(= 1,2-Bis(3,5-di(tertiarybutyl)-2-mercaptophenylthio) ethane (2-)) and PPh3, CO, PMe3, NH3, and N2H4 ColigandsThe coordination properties of the sterically demanding thioether-thiolate ligand ‘buS4’2- (= 1,2-Bis(3,5-di(tertiarybutyl)-2-mercaptophenylthio)ethane (2-)) towards Ruthenium were investigated. [Ru(PPh3)2 (‘buS4’)], 1, was obtained from [RuCl2(PPh3)3] and ‘buS4’—Li2. One PPh3 ligand in 1 is labile towards substitution and can be exchanged by L = CO (2), PMe3 (3), or NH3 (5) yielding [Ru(L)(PPh3)(‘buS4’)]. The PMe3 complex [Ru(PMe3)2(‘buS4’)], 4, is thermically inert as well as 2, 3, and [Ru(CO)2(‘buS4’)], 6, which was obtained from [RuCl2(CO)3THF] and ‘buS4’—Li2. Considering the thermical reaction inertness of 6, its fast reaction with N2H4 yielding [Ru(N2H4) (CO) (‘buS4’)], 7, is remarkable; the reaction probably takes place via 19e- intermediates. All ‘buS4’ complexes are better soluble in organic solvents than the corresponding [Ru(‘S4’)] parent compounds, their ν(CO)frequencies or 31PNMR shifts, however, are nearly identical, allowing the conclusion that the influence of the t-butyl groups is topological and not electronic. All now complexes were characterized by elemental analyses as well as IR, NMR, and mass spectroscopy.
    Notes: Die Koordinationseigenschaften des sterisch anspruchsvollen Thioether-Thiolat-Liganden ‚buS4‘2- (= 1,2-Bis(3,5-di(tertiärbutyl)-2-mercaptophenylthio)ethan (2-)) gegen-über Ruthenium wurden untersucht. Dabei wurde [Ru(PPh3)2(‚buS4‘)], 1, aus [RuCl2(PPh3)3] und ‚buS4‘—Li2 erhalten. Ein PPh3-Ligand in 1 ist substitutionslabil und kann durch L = CO (2), PMe3 (3 oder NH3 (5) unter Bildung von [Ru(L)(PPh3))(‚buS4‘)] ersetzt werden. Der zu 1 analoge PMe3-Komplex [Ru(PMe3)2(‚buS4‘)], 4, ist thermisch inert, ebenso wie 2, 3 und [Ru(CO)2(‚buS4‘)], 6, das aus [RuCl2 (CO)3THF] und, ‚buS4‘—Li2 erhalten wurde. In Anbetracht der thermischen Reaktionsträgheit von 6 ist seine rasche Reaktion mit N2H4 zu [Ru(N2H4)(CO)(‚buS4‘)], 7, bemerkenswert; die Reaktion verläuft wahrscheinlich über 19e--Zwischenstufen. Alle ‚buS4‘-Komplexe sind in organischen Lösungsmitteln besser löslich als ihre [Ru(‚S4‘)]-Stammverbindungen, n̈(CO)-Frequenzen oder 31P-Verschiebungen sind jedoch nahezu identisch, woraus auf einen topologischen, nicht aber elektronischen Einfluß der t-Butylgruppen geschlossen werden muß.Alle neuen Komplexe wurden elementaranalytisch sowie IR-, NMR- und massenspektroskopisch charakterisiert.
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  • 94
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 577 (1989), S. 293-300 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complex Formation of Copper(II) with Opioid PeptidesComplex compounds of copper(II) with the neuropeptide enkephaline were detected as CuH-(n-1)L + nLi+ ions by means of FAB mass spectrometry. Formation constants of proton and copper(II) complexes of four opioid peptides (L-I — L-IV) were determined potentiometrically. Complexes with methionine-containing ligands show the highest stability. Under physiological pH values all brain-existent enkephaline may be bound by endogeneous copper provided that [Cu2+] 〉 10-7 M.
    Notes: Mit Hilfe der FAB-Massenspektrometrie werden die Komplexverbindungen des Kupfer(II) mit dem Neuropeptid Enkephalin als Ionen der Zusammensetzung CuH-(n-1)L + nLi+ registriert. Die Protonierungs- und Komplexbildungskonstanten von vier Oligopeptiden bzw. ihren Kupfer(II)-Komplexen (L-I — L-IV) werden durch potentiometrische Titration ermittelt. Die höchste Stabilität zeigen Komplexe mit methioninhaltigen Liganden. Bei physiologischen pH-Werten kann das gesamte im Gehirn enthaltene Enkephalin an endogenem Kupfer bei [Cu2+] 〉 10-7 M gebunden sein.
    Additional Material: 4 Ill.
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  • 95
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 572 (1989), S. 135-139 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloaddition Reactions in the System 2-Isocyanato-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane/1,1,1,5,5,5-Hexafluor-4-trimethylsiloxy-3-pentene-2-oneThe two title compounds react to give in a (3+2) cycloaddition the spiro iminophosphoran 3 and its dimer 4, respectively. The (2+2) cycloaddition of hexafluoracetone and 3 yields the oxazaphosphetane 5, which decomposes rapidely into the Staudinger product 6. The hydrolytical cleavage of the trimethylsilyl group furnishes the tricyclic phosphorane 7. The 3JPH coupling in 3 is surprisingly large (51.6 Hz).
    Notes: Die beiden Titelverbindungen ergeben in einer (3+2)-Cycloaddition das Spiroiminophosphoran 3 bzw. dessen Dimeres 4. Eine (2+2)-Cycloaddition von Hexafluoraceton an 3 läßt das Oxazaphosphetan 5 entstehen, das rasch in das Staudinger-Produkt 6 zerfällt. Über die hydrolytische Abspaltung der Trimethylsilylgruppe von 3 wird das tricyclische Phosphoran 7 erhalten. Die Kopplungskonstante 3JPH in 3 von 51,6 Hz ist überraschend groß.
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  • 96
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 577 (1989), S. 283-292 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Basic Metals. LXIV. Lewis-basic Bis(trimethylphosphine)cobalt Complexes with Indenyl and Trifluormethylcyclopentadienyl as LigandsThe half-sandwich type compounds C9H7Co(PMe3)2 (1) and (C5H4CF3)Co(PMe3)2 (6) are prepared from CoCl(PMe3)3 and C9H7Li or TlC5H4CF3, respectively. They behave like metal bases and react with HBF4, CH3I (or CF3SO3CH3), I2, and CH3COCl by oxidative addition to give the cationic complexes [C9H7CoX(PMe3)2]+ and [(C5H4CF3)CoX(PMe3)2]+ (X = H, CH3, I, COCH3) which are isolated as the PF6 salts (2-5 and 7-10). The 1HNMR and the IR spectra of the compounds 1-10 are discussed, also in comparison to those of the corresponding cyclopentadienylcobalt complexes.
    Notes: Die Halbsandwichverbindungen C9H7Co(PMe3)2 (1) und (C5H4CF3)Co(PMe3)2 (6) werden aus CoCl(PMe3)3 und C9H7Li bzw. TlC5H4CF3 synthetisiert. Sie verhalten sich wie Metall-Basen und reagieren mit HBF4, CH3I (oder CF3SO3CH3), I2 und CH3COCl unter oxidativer Addition zu den kationischen Komplexen [C9H7CoX(PMe3)2]+-und [(C5H4CF3)CoX(PMe3)2]+ (X = H, CH3, I, COCH3), die als PF6-Salze (2-5 und 7-10) isoliert werden. Die 1H-NMR- und IR-Daten der Verbindungen 1-10 weden, auch im Vergleich zu denen der entsprechenden Cyclopentadienylcobalt-Komplexe, diskutiert.
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  • 97
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Selective Cyclotetramerization of Propargylic Alcohol: Catalytic Reactions with High Selectivity and Reaction Rate by Nickel ComplexesIt is shown propargylic alcohol reacts with different nickel catalysts to form cyclotetrameres in a selective reaction. Main product of the reaction is 1,3,5,7-tetrakis(hydroxymethyl)-cycloocta(1,3,5,7)-tetraene.The reaction is extremely fast; when it is carried out without solvents at 114°C turnover numbers of 106 catalytic cycles/mol Ni × h can be observed. The influence of phosphines is different: In solvents aromatic compounds, and cyclotetrameres are formed, when solvents are not used, phosphines have no controlling effect.The reaction can also be catalyzed by iron complexes to form cyclotetrameres, cobalt complexes yield a mixture of cyclotrimeres and cyclotetrameres.Supported Nickel or Raney-Nickel can also catalyze the cyclotetramerization.The investigations show that the 1-azadiene ligands in bis(cinnemaldehydeanil)-nickel(0) are substituted by propargylic alcohol in a fast reaction. After the substitution the catalytic reaction takes place at “ligand free nickel”.
    Notes: Es wird gezeigt, daß Propargylalkohol an vielen Nickelkatalysatoren selektiv zu Cyclotetrameren umgesetzt werden kann. Hauptprodukt der Reaktion 1,3,5,7-Tetrakis-(hydroxymethyl)-cycloocta(1,3,5,7)-tetraen. Die Reaktion ist extrem schnell; wenn ohne Lösungsmittel bei 114°C gearbeitet wird, können 106 katalytische Cyclen/Mol Ni × h erreicht werden. Der Einfluß von Phosphinen auf die katalytische Reaktion ist unterschiedlich: In Lösungsmitteln werden zunehmend Aromaten gebildet, wenn ohne Verwendung von Lösungsmitteln gearbeitet wird, haben Phosphine keinen steuernden Effekt.Die Reaktion kann auch durch Eisen(II)-Verbindungen katalysiert werden, während Cobaltkomplexe ein Gemisch von Cyclotrimeren und Cyclotetrameren bilden.Elementares Nickel auf Trägern oder Raney-Nickel können ebenfalls die katalytische Cyclotetramerisierung auslösen.Die Untersuchungen zeigen, daß 1-Azadienliganden in Bis(zimtanil)-nickel(0) in einer schnellen Reaktion durch Propargylalkohol substituiert werden. Nach der Substitution findet die katalytische Reaktion am „ligandfreien Nickel“ statt.
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  • 98
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Silylphosphanes with an Admantane Skeleton Formed in Reactions of P4 and Na/K with Dichlorsilanes, and their 31P NMR SpectraThe reactions of P4 and Na/K (molar ratio 1:3) with EtMeSiCl2, Et2SiCl2, and PhMeSiCl2 give access to the silylphosphanes with adamantane structure (EtMeSi)6P4 1, (Et2Si)6P4 2, and (PhMeSi)6P4 3. Likewise, the Si-functional adamantanes [Vinyl(Me)Si]6P4 4, (MeHSi)6P4 5, and (MeHSi)(Et2Si)6P4 6 can be obtained by the reaction of alkali phosphides with Vinyl(Me)SiCl2, MeHSiCl2, or Et2SiCl2/MeHSiCl2 (molar ratio 5:1), respectively. The compounds form colorless crystals (3 crystallies reluctantly). The reactions of the alkali phosphides with t-Bu2SiCl2 and Ph2SiCl2 do not lead to the corresponding adamantanes; t-Bu2SiCl2 doesn't react product mixture of the more reactive Ph2SiCl2 traces of (Ph2Si)6P4 could not be detected. The 31P-NMR-spectra of the compounds 1-6 are interpreted.
    Notes: Durch Umsetzung von P4 und Na/K (Molverhältnis 1:3) mit EtMeSiCl2, Et2SiCl2, PhMeSiCl2 werden die Silylphosphane mit Adamantanstruktur (EtMeSi)6P4 1, (Et2Si)6P4 2, (PhMeSi)6P4 3 zugänglich. Entsprechend lassen sich die Si-funktionellen Adamantane [Vinyl(Me)Si]6P4 4, (MeHSi)6P4 5 und (MeHSi)(Et2Si)5P4 6 durch Umsetzung des Alkaliphosphides mit Vinyl(Me)SiCl2; MeHSiCl2 bzw. Et2SiCl2/MeHSiCl2 (Molverhältnis 5:1) darstellen. Die Verbindungen sind kristallin (3 kristallisiert nur schwer). Die Umsetzungen des Alkaliphosphides mit (t-Bu)2SiCl2 und Ph2SiCl2 führen nicht zu den entsprechenden Adamantanen; (t-Bu)2SiCl2 reagiert unter den Darstellungsbedingungen der übrigen noch nicht, und in den Reaktionsprodukten des reaktionsfähigeren Ph2SiCl2 konnte das (Ph2Si)6P4 nicht nachgewiesen werden. Die 31P-NMR-Spektren der Verbindungen 1-6 werden interpretiert.
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 572 (1989), S. 181-185 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: About BaNiDy2O5 and BaNiLu2O5 with Octahedral and Tetragonal Pyramidal Coordinated Ni2+(I) BaNiDy2O5 and (II) BaNiLu2O5 were prepared for the first time and investigated by X-ray single crystal technique. [I: a = 3.773; b = 5.777; c = 11.352 Å; Z = 2; space group D2h25 - Immm; II: a = 6.931; b = 12.109; c = 5.634 Å; Z = 4; space group D2h16-Pbnm]. I crystallizes with an octahedral coordination of Ni2+ by O2-, II on the contrary is surrounded by a tetragonal pyramidal oxygen environment. II belongs to the series of BaCuLn2O5 compounds.
    Notes: (I) BaNiDy2O5 und (II) BaNiLu2O5 wurden erstmals dargestellt und mit Einkristallröntgenbeugungsmethoden untersucht [I: a = 3,773; b = 5,777; c = 11,352 Å; Z = 2; Raumgruppe D2h25-Immm; II: a = 6,931; b = 12,109; c = 5,634 Å; Z = 4; Raumgruppe D2h16-Pbnm]. I kristallisiert mit oktaedrisch koordiniertem Ni2+, II dagegen mit der Koordinationszahl 5 in Form einer tetragonalen Pyramide. II gehört somit zur Reihe der BaCuLn2O5-Verbindungen.
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 572 (1989), S. 151-163 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Characterization of the trans-Dioxoosmates, [OsO2(CN)2X2]2-, X = NCO, NCS, SeCN, 1/2 (C2O4); [OsO2(CN)2X2)], X = py, 1/2 bipy and [OsO2(CN)2X]22-, X = OH, OCH3By careful acidification of the aqueous solution of [OsO2(OH)4]2- in the presence of the required amount of cyanide ions with oxalic acid or acetic acid the osmyl complexes [OsO2(CN)2(C2O4)]2- or [OsO2(CN)2(OH)]22- are prepared for the first time, respectively. By acidolytic ligand substitution from [OsO2(CN)2(OH)]22- the new compounds [OsO2(CN)2(OCH3)]22-, [OsO2(CN)2(NCO)2]2-, [OsO2(CN)2(NCS)2]2-, [OsO2(CN)2(SeCN)2]2-, [OsO2(CN)2(py)2], and [OsO2(CN)2(bipy)] are formed. The IR and Raman spectra are assigned assuming D2h or C2v local symmetry. In respect to the relative high frequencies of vCO and vCS coordination via N is deduced for NCO and NCS, whereas the low vCSe frequency gives evidence for Se linkage of the SeCN. At 10 K the absorption spectra reveal a distinct vibrational fine structure. The excitation of one electron from the ground state of OsVI, 1Ag[ag2](dxy), D2h, or 1A1[a12](dxy), C2v, into the lowest unoccupied b2g/b3g or b1/b2 (dxz, dyz) orbitals gives triplet terms of lower energy (615-450 nm) and singlet terms at higher energy (475-390 nm). On both bands a progression of 723-757 cm-1 is superposed caused by coupling of the d—d transition with vas(Os = O). Two more intense absorptions in the UV region are assigned to charge transfer transitions from pπ orbitals of the oxo ligands into the lowest unoccupied niveau at OsVI. The triplet terms are observed at 390-340, the singlet terms at 340-280 nm. The averaged progression of vibrational coupling with vs (Os = O) is 690-738 cm-1, the singlet triplet energy distances are in the order of 3 600 cm-1.
    Notes: Durch vorsichtiges Ansäuern der wäßrigen Lösung von [OsO2(OH)4]2- in Gegenwart der erforderlichen Menge Cyanidionen mit Oxalsäure bzw. Essigsäure sind die Osmylkomplexe [OsO2(CN)2(C2O4)]2- bzw. [OsO2(CN)2(OH)]22- erstmals hergestellt worden. Durch acidolytische Ligandensubstitution entstehen aus [OsO2(CN)2(OH)]22- die neuen Verbindungen [OsO2(CN)2(OCH3]22-, [OsO2(CN)2(NCO)2]2-, [OsO2(CN)2(NCS)2]2-, [OsO2(CN)2(SeCN)2]2-, [OsO2(CN)2(py)2] und [OsO2(CN)2(bipy)]. Die IR- und Raman-Spektren werden gemäß der lokalen Symmetrie D2h oder C2v zugeordnet. Aus der relativ hohen Frequenz von vCO und vCS wird für NCO und NCS die Koordination über N, aus der niedrigen Lage von vCSe die Koordination von SeCN über Se abgeleitet. Die an den festen Komplexen bei 10 K registrierten Absorptionsspektren zeigen eine ausgeprägte Schwingungsfeinstruktur. Bei Anregung eines Elektrons von OsVI aus dem Grundzustand 1Ag[ag2](dxy) bei D2h- bzw. 1A1[a12](dxy) bei C2v-Symmetrie in die niedrigsten, unbesetzten b2g/b3g- bzw. b1/b2-(dxz, dyz)-Orbitale entstehen energieärmere Triplett-Terme (615-450 nm), sowie energiereichere Singulett-Terme (475-390 nm). Die auf beiden Banden gefundene mittlere Progression von 723-757 cm-1 beruht auf der Kopplung des d-d-Übergangs mit vas (Os = O). Zwei viel intensivere Bandensysteme im UV-Bereich werden den Charge-Transfer-Übergängen von pπ-Orbitalen der Oxoliganden in das niedrigste unbesetzte Niveau am OsVI zugeordnet. Die Triplett-Terme werden bei 390-340, die Singulett-Terme bei 340-280 nm beobachtet. Die mittlere Progression der Schwingungskopplung mit vs(Os = O) beträgt 690-738 cm-1, die Singulett-Triplett-Abstände liegen bei 3 600 cm-1.
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