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  • 1
    ISSN: 0009-2940
    Keywords: Bis(phosphido)-bridged diiron hexa(penta)carbonyl complexes, molecular structures ; Steric strain ; Iron-iron double bond ; Calculations, EHT ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An Unusual Pair of Bis(phosphido)-Bridged Diiron Carbonyl Complexes: [Fe2(CO)n{μ-P(tBu)2}(μ-PCy2)] (n = 5 and 6)Treatment of Na[Fe2(CO)6(μ-CO){μ-P(tBu)2}] with Cy2PCl gives [Fe2(CO)6{μ-P(tBu)2}(μ-PCy2)] (1) which loses CO on heating in toluene to afford [Fe2(CO)5{μ-P(tBu)2}(μ-PCy2)] (2). Complexes 1 and 2 have been characterized spectroscopically and by X-ray analyses. The central Fe2P2 unit in 1 is exactly planar whereas in 2 it is somewhat folded.
    Additional Material: 3 Ill.
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  • 2
    ISSN: 0009-2940
    Keywords: M2P2 tetrahedral complexes ; Phosphido ligand complexes as intermediates ; Ni2P4O distorted prismane framework ; CO incorporation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexes with Metal-Phosphorus Triple Bonds as Possible Intermediates in the Reactions between Chlorophosphinidenes and Metalates of Various Transition MetalsThe reaction of [{M′(CO)5}2PCl] (M′ = Cr, W) with various metalates ([Cp′Mo(CO)3]-, [Cp * Ni(CO)]-, [Cr2(CO)10]2-) yields the M2P2 tetrahedral complexes [(MLn)2(μ,η2- P2){M′(CO)5}2] (MLn = Cp*Ni, M′= Cr (1), W (2); MLn = Cp′Mo(CO)2, M′ = Cr (4); Cp* = η5-C5Me5, Cp* = η5C5H3tBu2) and the cyclo-P4 compound [{Cr(CO)4}(η4-P4){Cr(CO)5}4] 6. As side products the distorted prismane [(Cp*Ni)2{μ4,η4-(P2-O-P2)}{W(CO)5}2] 3 and the diphosphino-methanone complex [{Cp′Mo(CO)2}2{μ4η2-PC(O)P}-{Cr(CO)5}2] 5 are formed. The complexes are characterised by NMR, IR, MS, and X-ray structure analysis (1-5). Studying the reaction pathway provided evidence of phosphido intermediates of the type [LnM≡P→M′Ln].
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0009-2940
    Keywords: P ligands ; P-P bond formation reaction ; Molybdenum ; Chromium ; Nickel ; Carbonyl complexes ; Main group elements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [Cr(CO)5PCl3] reacts with different metallates K[CpxMo(CO)3] [Cpx = ·5-C5H4tBu (Cp]), ·5-C5H3tBu2-1,3 (Cp))], K[CpFe(CO)2], K[Cp]Cr(CO)3], K[C}*Ni(CO)] and Na2[Cr2(CO)10] at -78°C in THF to yiel various P2, cyclo- P3 and cyclo-P5 ligand complexes of the formulae [Cp] Mo(CO)2 (.2-P3)] (1a), [Cp]Mo(CO)2(.3-P3)] (1b), [{CP'Mo-(CO)2}2(μ,.2-P2)] (2a), [{Cp]Mo(CO)2}2(μ, ·2-P2)] (2b), [Cp]Fe).5-P5)] (3), [(Cp'Cr)2(μ,.5-P5)] (4), [{Cp]Cr(CO)2}2-(μ,.2-P2)] (5), [(Cp*Ni)2(μ,.2-P2){Cr(CO)5}2] (6). [{(CO)5Cr}Cl2PPCl2{Cr(CO)5}] (7) and [{Cr(CO)5}2PCl (8). Comprehensive studies of the reaction pathway leading to formation of the cyclo-P3 product 1a give strong indications that a sequence involving metal-halogen exchange and stepwise P-P bond formation takes place, proceeding via [{CO}5Cr}Cl2PPCl2{Cr(CO)5}] (7) and the cyclo-P3 precursor compond [{Cp]Mo(CO)3}{Cp'Mo(CO)2}2{Cr(CO)5}(μ,.3:1:1-P3)] (9). The latter two complexes have been isolated and structurally characterized.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 108 (1975), S. 291-300 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Directed Synthesis of Sulfinato-O and -S Complex of Transition Metals, XI. Linkage Isomerism in Sulfinato Complexes of Zinc(II)Starting from the sulfinato-O, O′ complexes (RSO2)2Zn(OH2)2(1a, b) the mono-, bis-, and tris(2, 2′-bipyridyl) complexes 2a, b, 3a, b, and 4a, b are produced according to equation (1) by stepwise addition of 2, 2′-bipyridyl. In the case of the bis(2, 2′-bipyridyl) complexes 3a, b the linkage-isomeric sulfinato-O and -S complexes 3aO, 3bO, and 3aS, 3bS are obtained. From 4a, b 1 mole of 2, 2′-bipyridyl can be eliminated reversibly with acetone according to equation (7) with formation of 3aO and 3aO. The newly prepared compounds were characterized on the basis of their i. r. spectra. In the case of 4a, b DTA, TG, and DTG measurements were carried out.
    Notes: Gemäß Gl. (1) gelingt, ausgehend von den Sulfinato-O, O′-Komplexen (RSO2)2zn(OH2)2 (1a, b), die schrittweise Addition von 2,2′-Bipyridyl, wobei die Mono-, Bis-und Tris(2,2′-bipyridyl)-Komplexe 2a, b, 3a, b und 4a, b entstehen. Im Falle der Bis(2,2′-bipyridyl)-Komplexe 3a, b wurden die bindungsisomeren Sulfinato-O-und-S-Komplexe 3aO, 3bO und 3aS, 3bs erhalten. Aus 4a, b läβt sich mit Aceton reversibel ein mol 2, 2′-Bipyridyl gemäß Gl. (7) unter Bildung von 3aO und 3bO abspalten /die neu dargestellten Verbindungen werden IR-spektroskopisch charakterisiert. Im Falle von 4a, b sind DTA-, TG- und DTG-Messungen durchgeführt worden.
    Additional Material: 1 Tab.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 190 (1930), S. 270-276 
    ISSN: 0863-1786
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Neben den1 Chlor-1-fluorid besteht auch ein Chlor-3-fluorid, welches durch Erhitzen von CI2 oder CIF mit überschüssigem F2 dar- gestellt wird. Die umkehrbare Reaktion CIF + F2 ⇆ CIF3 führt zu einem Gleichgewicht, in dem bei 250° Zahl der CIF-Moleküle ein Mehrfaches der CIF3-Moleküle ist. Die Zusammensetzung des neuen Fluorids is durch Analysen und Dichtebestimmungen sichergestellt. Seine physikalischen und chemischen Eigenschaften werden mit - geteilt.Besonders bemerkenswert ist die Lebhaftigkeit und die Mannigfaltigkeit der Reaktionen des CIF3.
    Additional Material: 1 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 557 (1988), S. 91-97 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: PPh4[As3S3Cl4] and PPh4[As3S3Br4]When As2S3 reacts with PPh4X and HX in 1,2-C2H4X2 (X = Cl, Br), the title compounds are obtained as minor products; the main products are PPh4[As2SX5]. Their crystal structures were determined by X-ray diffraction. PPh4[As3S3Cl4]: a = 1187.7, b = 1090.9, c = 1191.8 pm, α = 82.91, β = 88,93, γ = 88.52°; twins with twin plane (100); R = 0.109 for 1618 observed reflexions of one twin crystal. PPh4[As3S3Br4]: a = 1119.7, b = 1177.5, c = 1204.1 pm, α = 81.59, β = 85.88, γ = 88.25°; R = 0.061 for 2331 observed reflexions. Both compounds crystallize in the space group P1, Z = 2, and can be considered to be isotypic. Nevertheless, PPh4[As3S3Br4] does not form twins as PPh4[As3S3Cl4]. The crystals consist of PPh4+ and [As3S3X4]- ions. In the anions, the three As atoms of an As3S3 ring in the chair conformation are commonly joined to an X atom and each As atom is bonded to one further terminal X atom. Cations and anions are packed in alternating layers.
    Notes: Bei der Reaktion von As2S3 mit PPh4X und HX in 1,2-C2H4X2 (X = Cl, Br) entstehen die Titelverbindungen als Nebenprodukte; das Hauptprodukt ist jeweils PPh4[As2SX5]. Ihre Kristallstrukturen wurden durch Röntgenbeugung bestimmt. PPh4[As3S3Cl4]: a = 1187,7, b = 1090,9, c = 1191,8 pm, α = 82,91, β = 88,93, γ = 88,52°; Zwillinge nach (100); R = 10,9% für 1618 beobachtete Reflexe eines Zwillingsindividuums, die nicht mit Reflexen des anderen Individuums zusammenfallen. PPh4[As3S3Br4]: a = 1119,7, b = 1177,5, c = 1204,1 pm, α = 81,59, β = 85,88, γ = 88,25°; 2331 beobachtete Reflexe, R = 6,1%. Beide Verbindungen kristallisieren in der Raumgruppe P1 (triklin), Z = 2, und können als isotyp angesehen werden. Trotzdem bildet PPh4[As3S3Br4] im Gegensatz zu PPh4[As3S3Cl4] keine Zwillinge. Die Kristalle sind aus PPh4+-Ionen und [As3S3X4]--Ionen aufgebaut. Die Anionen bestehen aus einem As3S3-Ring in der Sesselkonformation, an jedes As-Atom ist ein terminales X-Atom gebunden und das vierte X-Atom ist an alle drei As-Atome gebunden. Kationen und Anionen sind in sich abwechselnden Schichten gepackt.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 859-864 
    ISSN: 0044-2313
    Keywords: 2,2-Bis(diisopropoxyphosphonyl)propyl methyltin dibromide ; synthesis ; crystal structure ; n.m.r. data ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Molecular Structure of 2,2-Bis(diisopropoxyphosphonyl)propyl Methyltin DibromideBy methylation of Me3SnCH2CH[P(O)(OPr-i)2]2 with NaH/MeI Me3SnCH2C(Me)[P(O)(OPr-i)2]2 (1) is obtained, which is converted by bromine into the dibromide MeBr2SnCH2C(Me)[P(O)(OPr-i)2]2 (2). An X-ray crystal structure analysis shows 2 to be monomeric. The tin atom is situated in the centre of a distorted octahedron, in which the functional substituent is intramolecular coordinated as tridentate ligand in a facial mode. The two organo groups are arranged in trans-position (C—Sn—C 155.1°), whereas the oxygen and bromine atoms are orientated cis to each other. The six-membered ring of the bicyclic molecular fragment of 2 which results from the coordination of the functional organo group to the tin atom shows a boat-conformation, whereas the two five-membered rings exist in twist-conformations. Multinuclear n.m.r. and i.r. data show that 2 retains its solid state structure also in nonpolar solvents.
    Notes: Durch Methylierung von Me3SnCH2CH[P(O)(OPr-i)2]2 mittels NaH/MeI erhält man Me3SnCH2C(Me)[P(O)(OPr-i)2]2 (1), das mit Brom in das Dibromid MeBr2SnCH2C(Me)[P(O)(OPr-i)2]2 (2) überführt wird. Nach der Röntgenkristallstrukturanalyse ist 2 im Festkörper monomer. Das Zinnatom befindet sich im Zentrum eines verzerrten Oktaeders, in dem der funktionelle Substituent intramolekular als tridentater Ligand in facialer Anordnung koordiniert ist. Die beiden Organoreste sind trans-ständig angeordnet (C—Sn—C 155,1°), während sich die Sauerstoff- und Bromatome in cis-Anordnung zueinander befinden. Der Sechsring des aus der Koordination des funktionellen Organorestes am Zinnatom resultierenden bicyclischen Molekülfragmentes von 2 weist Wannenkonformation auf, während die beiden Fünfringe in Twist-Konformationen vorliegen. Multikern-NMR- und IR-Daten belegen, daß 2 seine Festkörperstruktur auch in unpolaren Lösungsmitteln beibehält.
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 63-71 
    ISSN: 0044-2313
    Keywords: diethyl triorganostannylmethyl N-acyl aminomalonates ; ethyl 3-(trimethylstannyl)-N-acyl alaninates ; 1,2-oxastannolane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: C-Stannylmethylated N-Acetyl- and N-Formyl-aminomalonic Acid DerivativesTin compounds of the type Me3SnCH2C(NHCOR) · (COOEt)2 (1: R = CH3; 2: R = H) are synthesized by reaction of acylaminomalonates with iodomethyl trimethylstannane. The halogenation of 1 and 2 yields the halostannylsubstituted compounds Me3-nXnSnCH2C(NHCOR)(COOEt)2 3-6 (R = Me, H; n = 1, 2; X = Cl, Br). The decarbethoxylation (KRAPCHO reaction) of 1 and 2 gives ethyl 3-(trimethylstannyl)-N-acyl alaninates (7 and 8). With one equivalent KOH 1 and 2 are transformed into the monoethyl malonates of the type Me3SnCH2C(NHCOR)(COOH)(COOEt) (9: R = CH3), which convert simultaneously under decarboxylation into 7 and 8 and by cyclisation under elimination of methane into the 1,2-oxastannolane derivatives 10 and 11. IR, NMR data and the determination of the crystal structure reveal for MeBr2SnCH2C(NHCOCH3)(COOEt)2 (5) hexacoordinated tin by intramolecular coordination of the amide-CO and one of the ester-CO groups.
    Notes: Zinnverbindungen des Typs Me3SnCH2C(NHCOR)(COOEt)2 (1: R = CH3; 2: R = H) werden durch Umsetzung von Acylaminomalonsäureestern mit Iodomethyltrimethylstannan dargestellt. Die Halogenierung von 1 und 2 liefert die halogenostannylsubstituierten Verbindungen Me3-nXnSnCH2C(NHCOR)(COOEt)2 3-6 (R = Me, H; n = 1, 2; X = Cl, Br). Die Decarbethoxylierung (KRAPCHO-Reaktion) von 1 und 2 führt zu 3-(Trimethylstannyl)-N-acyl-alaninethylestern (7 und 8). Mit einem Äquivalent KOH werden 1 und 2 in die Monoethylester des Typs Me3SnCH2C(NHCOR)(COOH)(COOEt) (9: R = CH3) überführt, die sich in Folgereaktionen sowohl unter Decarboxylierung zu 7 bzw. 8 als auch durch Cyclisierung unter Methanabspaltung zu den 1,2-Oxastannolanderivaten 10 bzw. 11 umwandeln. IR-, NMR-Daten und die Bestimmung der Kristallstruktur beweisen für MeBr2SnCH2C(NHCOCH3)(COOEt)2 (5) hexakoordiniertes Zinn durch intramolekulare Koordination der Amid-CO- sowie einer Ester-CO-Gruppe.
    Additional Material: 2 Ill.
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  • 9
    ISSN: 0044-2313
    Keywords: Cyanamidocarboxylate complexes ; IR ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pseudoelement Compounds VII. [1] Crystal and Molecular Structure of Tris(ethylenediamine)nickel(II)-bis(2-methyl-4-chlorophenoxy-cyanamidoacetate)Surprisingly, in the presence of ethylenediamine 2-methyl-4-chlorphenoxy-cyanamidoactetate reacts with nickel(II) and copper(II) ions preferentially under formation of complexes of the type [M(en)3]X2. The IR spectra and the X-ray diffraction investigations corresponding to [Ni(en)3][2-Me-ClC6H3OCH2C(O)NCN]2 show that two cyanamidocarboxylate ions [RC(O)NCN]- are bonded to the complex cation through, in each case, two N—H … O=C hydrogen bonds between NH protons of ethylenediamine ligands and the carbonyl oxygen atoms. Additionally, in the crystal weak N—H … N≡C bridges were found between the nitrile nitrogen atoms of the anions and NH protons of neighbouring complex cations.
    Notes: 2-Methyl-4-chlorphenoxy-cyanamidoacetat bildet zu unserer Überraschung mit Nickel(II)- und Kupfer(II)-Ionen in Gegenwart von Ethylendiamin bevorzugt Komplexe der Zusammensetzung [M(en)3]X2. IR-spektroskopische Messungen und die Kristallstruktrukturuntersuchung an [Ni(en)3][2-Me-4-ClC6H3OCH2C(O)NCN]2 zeigen, daß zwei Cyanamidocarboxylat-Anionen [RC(O)NCN]- über jeweils zwei N—H … O=C-Wasserstoffbrückenbindungen zwischen N—H-Protonen der Ethylendiamin-Liganden und den Carbonyl-Sauerstoffatomen an ein komplexes Kation [Ni(en)3]2+ gebunden sind. Im Kristall liegen außerdem noch schwache N—H … N≡C-Brücken zwischen Nitril-N-Atomen der Anionen und NH-Protonen benachbarter komplexer Kationen vor.
    Additional Material: 2 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 444 (1978), S. 217-236 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Correlations between Properties of Chalcogenide Glasses. V. Glass Formation and Phase Separation in the Systems Tl—Ge—Se und Pb—Ge—SeThe glass formation in the systems Tl—Ge—Se and PbSe—GeSe2—Se is investigated applying defined melting conditions. In both systems exist - at high Se and low Ge contents - large regions of liquid immiscibility and microphase separation. The compositions of the interconnected phases were determined by chemical analysis, scanning electron microscopy, and by measurements of Vickers hardness. Transformation temperatures Tg and hardness numbers HMV of homogeneous Tl—Ge—Se glasses are in a linear relationship with the approximate values ΔAH1 for the atomization energies of the samples.
    Notes: Für definierte Schmelzbedingungen wird die Glasbildung in den Systemen Tl—Ge—Se und PbSe—GeSe2—Se beschrieben. Bei hohen Selen- und geringen Germaniumgehalten treten in beiden Fällen ausgedehnte Gebiete mit Mikro- und Makrophasentrennung auf. Zur Festlegung des Konnodenverlaufs in den Mischungslücken werden naßchemische Analysen, rasterelektronenmikroskopische Untersuchungen und Mikrohärtemessungen herangezogen. Für die Transformationstemperaturen Tg und die Mikrohärten HMV homogener Tl—GE—Se-Gläser ergeben sich lineare Abhängigkeiten von den Näherungswerten ΔAH1 für die molare Atomisierungsenthalpie der Proben.
    Additional Material: 7 Ill.
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