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  • 11
    Electronic Resource
    Electronic Resource
    Reversible [4 + 1]-Selbstaddition von Alkyl(arylimino)phosphanen und regioselektive Cycloaddition mit (E)- und (Z)-Azobenzol (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 2635-2640 
    Details
    ISSN: 0009-2940
    Keywords: Alkyl(arylimino)phosphanes ; [4 + 1] Selfaddition reactions ; [n + 1] Cycloaddition reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reversible [4 + 1] Selfaddition of Alkyl(arylimino)phosphanes and Regioselective Cycloaddition to (E)- and (Z)-AzobenzeneDehydrohalogenation of the amino(chloro)phosphanes RP(Cl)N(H)Aryl (1; R=Me, Et; Aryl = 2,4,6-Tri-tert-butylphenyl) affords the corresponding iminophosphanes RP= NAryl (2) which undergo a reversible [4 + 1] selfaddition with participation of the aryl substituent to form 3,3a-Dihydro-2H-1,2,3λ5-benzoazadiphospholes 3. The regioselective cycloaddition of 2b towards (E)- and (Z)-azobenzene (4a and b) has been demonstrated in the formation of two different phospholes 6 and 8 which are formed by a [2 + 1] and [4 + 1] cycloaddition reaction of the iminophosphane 2b. The structure of the fiveymembered ring systems 3, 6 and 8 has been elucidated by NMR spectroscopy and single-crystal X-ray studies of 3b and 6.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921251203
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  • 12
    Electronic Resource
    Electronic Resource
    Methylenphosphanyl-Komplexe von Chrom, Molybdän, Wolfram, Eisen und Nickel: Synthese und ReaktionenHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1299-1309 
    Details
    ISSN: 0009-2940
    Keywords: Methylenephosphanyl complexes ; Phosphenium complexes ; Phosphavinylidene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methylenephosphanyl Complexes of Chromium, Molybdenum, Tungsten, Iron and Nickel - Synthesis and ReactivityHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet.The reaction of the functionalized P/C double bond systems X - P=C(R)SiMe3 [R=SiMe3 and X=Cl (1a), Cp* (5a) or R=Ph and X=Br (1b), Cp* (5b)] with alkali carbonylmetallates or carbonyl complexes of group 6, 8, and 10 metals leads to the formation of the transition metal-substituted phosphaalkenes [{M} - P=C(R)SiMe3 3a - j and 4a - i], in which the P - C fragment acts as a one-electron donor. Depending on the nucleophilicity of the transition metal anion used, but also on the methylene carbon substituents [1a: (SiMe3)2: 1b: (Ph)1-SiMe3], a different stability of the (methylenephosphanyl)1-metal complexes is observed, which results in a broad spectrum of reactivities. As demonstrated by the reactions of the (methylenephosphanyl)metal complexes with sulfonic acid derivatives (10a - c), diverse transition metal complexes (11a - c), as well as chalcogenes (14a - c, 15), a change in the reactivity is observed, indicating a transition from an olefinic to a carbenic character of the methylenephosphane. In comparison to the phenyl-substituted derivatives 4a - i the bis(trimethyl)1-substituted species 3a - j exhibit an increased reactivity. This is reflected in the easy decarbonylation of 3a - d to the phosphavinylidene complexes 12a - d.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260606
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  • 13
    Electronic Resource
    Electronic Resource
    Synthese, Struktur und dynamisches Verhalten von 1,3,5-Triaza-2,4-diphospha-1,4-pentadienenVorgetragen auf der XIth International Conference on Phosphorus Chemistry, Tallinn, USSR, July 1989. (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 797-799 
    Details
    ISSN: 0009-2940
    Keywords: 1,3,5-Triaza-2,4-diphospha-1,4-Pentadienes, dynamic behavior ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis, Molecular Structure, and Dynamic Behaviour of 1,3,5-Triaza-2,4-diphospha-1,4-pentadienesChloro(arylimino)phosphane (1) reacts with the 1,3-diaza-2-phosphaallylic system 3 to form 1,3,5-triaza-2,4-diphospha-1,4-pentadienes Ar-N=P-N(R)-P=N-Ar (Ar = 2,4,6-tBu3-C6H2; R = tBu, 2,4,6-iPrc3C6H2) (4a-c). the molecular structure of 4a (“Exo-endo-S conformation”) as well as the dynamic behaviour of the compounds in solution are discussed. the observed temperature dependance of the NMR spectra of 4c was interpreted as a sigmatropic 1,3-rearrangement followed by a P-N rotation.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230425
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  • 14
    Electronic Resource
    Electronic Resource
    Untersuchungen am System Phosphirenimin/Iminophosphan  -  Insertionsreaktionen und Isomerisierung (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 313-319 
    Details
    ISSN: 0009-2940
    Keywords: Phosphirene imines ; 1,2-Diphosphete diimines ; Isomerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations of the System Phosphirene Imine/Iminophosphane - Insertion and Isomerization ReactionsTreatment of the iminophosphanes R1P=NR2 1 [R2 = tBu, R1 = Et3C (a); R2 = Aryl, R1 = Et (b), Me (c)] with 1,4-diphenyl-butadiyne (2) leads to the phosphirene imines R1-(R2N=)P̌(Ph)=CCCPh 3a-c and [R1(R2N=)P̌(Ph)=CC]2 4a-c. Further reaction with 1a, c gives the 1,2-diphosphetes R1(R2N=)PP(R1)(=NR2)C(Ph)=CCCPh 5a, b, which isomerize in the case of R1 = Me into the triphosphabicyclo[3.2.0]-hepta-1,6-diene 7. In the reaction of the phosphirene imines R1(ArylN=)P̌(R2)=C(R2) 3 [R1 = Me, R2 = Ph (d); R1 = Et, R2 = COOMe (e)] with the iminophosphanes 1b, d the initially formed diphosphetes 9a, b isomerize to the 1,2-diazaphosphole Cl(Mes*N=)PN(Mes*)P(Me)C(Ph)=C(Ph) 10 or the dioxadiphosphabicyclooctadiene C=C(OMe)OP(=N-Mes*)(Et)C=C(OMe)OP(=NMes*)(Et) 12 depending on the substituents. A reaction of the phosphirene imine 3d with dimethylamino-borane furnishes the vinylphosphane. Ph(H)C=C(Ph)P(Et)N(H)Mes* (14) by ring opening. The compounds 7, 10, 12 have been characterized by X-ray structure analyses.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270206
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  • 15
    Electronic Resource
    Electronic Resource
    Chirale dreilagige und kondensierte [2.2]Cyclophane Synthese, Struktur, Chiroptik (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 169-176 
    Details
    ISSN: 0009-2940
    Keywords: Caesium effect / Chiroptical properties / Circular dichroism / Cyclophanes, multilayered ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral Triple-Layered and Condensed [2.2]Cyclophanes - Synthesis, Structure, Chiroptical PropertiesThe helical title compounds 1-5 are obtained using a simple one-step cyclisation reaction with yields reaching or increasing those obtained by application of organometallic methods in [2.2]phane syntheses. The formation of the triple-layered phanes 1 leads with high selectivity only to the “up-down” isomers with fixed conformation, as shown by X-ray crystallography and by the detection of strong NOEs of the inner hydrogen atoms. For studies on structure-chiroptic relation-ships a systematic sequence of helical [2.2]phanes with larger arene systems is synthesized. Enrichment of enantiomers is achieved by HPLC on (+)-PTrMA; the kinetics of racemisation and the CD spectra are discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230129
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  • 16
    Electronic Resource
    Electronic Resource
    Synthese und Kristallstruktur von Iminophosphanen mit Liganden hoher π-Donorfähigkeit (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 477-479 
    Details
    ISSN: 0009-2940
    Keywords: Phosphines, imino- / P-Heterobutadienes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Crystal Structure of Iminophosphanes Containing Ligands with High π-Donor AbilityReaction of the lithiated ketimines LiN=CR2 (R2 = tBu2, fluorenyl) 1a,b with the chloro(arylimino)phosphanes Cl-P=N-Ar (AR = 2,4,6-tBu3C6H2) 2 affords the heterobutadienes R2C=N-P=NAr 3a,b. The X-ray structure determination of 3a,b reveals an unusually short P-N single bond both cis and trans arrangements of the NPN skeleton.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230311
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  • 17
    Electronic Resource
    Electronic Resource
    Halogen(Silyl)phosphane - Synthese und Eigenschaften (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1245-1251 
    Details
    ISSN: 0009-2940
    Keywords: Phosphanes, halogeno(silyl)- ; Diphosphiranes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Halogeno(si1yl)phosphanes - Synthesis and PropertiesBis(trimethylsilyl)phosphanes 1a-d react with hexachloroethane to give chloro(trimethylsily)phosphanes 2a-d. The decomposition of these compounds to cyclophosphanes is found to be catalized by Lewis acids and bases. Nucleophilic substitution of the P-chloro function of 2c leads to the bromo(9a), iodo- (9b) and azido derivative (10a). Methanolysis of 2a-d leads to tye secondary chlorophosphanes 11a-d.Reaction of 2a-e with chloromethylenephosphane 12a results in the formation of 1-chlorodiphosphiranes 16a-e via a 1,2-diphospha-2-propene intermediate 14. The 1-bromo-(19a) and 1-iododiphosphirane 19b is accessible from 16c by exchange reaction with the corresponding halosilanes. The potential of halo(sily)phosphanes as phosphanediyl transfer reagents was unhindered in the reaction of 2c with different substituted phosphaalkenes 28a-d to the corresponding diphosphiranes 29a- d.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230606
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  • 18
    Electronic Resource
    Electronic Resource
    Ein Weg zu neuartigen funktionalisierten Bis(imino)phosphoranen XP(= NAryl)=NAlkyl (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 2329-2333 
    Details
    ISSN: 0009-2940
    Keywords: 1H-Tetraphospholes, 4,5-dihydro- ; Bis(imino)phosphoranes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Route to Novel Functionalized Bis(imino)phosphoranes XP(=NAryl)=NAlkylChloro(arylimino)phosphane (1) reacts with alkyl azides RN3 (R = tBu, Et3C, 1-Ad) to form 4,5-dihydro-1H-tetrazaphos-pholes 2a-c. The thermal decomposition of these compounds results in the formation of the diazadiphosphetidines 4a-c via the chlorobis(imino)phosphorane intermediates 3a-c, which were detected by NMR spectroscopy. By treating 2a with the lithium salts Li(nBu, C5Me5, NHAryl, OAryl, tBuS) the 4,5-dihydro-1H-tetrazaphosphole intermediates 5a-d are obtained, which by elimination of nitrogen form the bis(imino)phosphoranes 6a-e. The X-ray structure determination of the phosphane derivative tBu2P—P(=NCEt3)= NAryl (7), obtained by the same procedure, is discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901231216
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  • 19
    Electronic Resource
    Electronic Resource
    Redox Properties of Diphosphanes (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1563-1565 
    Details
    ISSN: 0009-2940
    Keywords: Diphosphanes ; Cyclic voltammetry ; Calculations, MNDO, ab initio ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diphosphanes undergo electrochemical one-electron oxidation. In case amino groups are at the phosphorus, the resulting distonic diphosphane radical cations disproportionate readily into a dication and a diphosphane; the former separates into two phosphenium cations.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240713
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  • 20
    Electronic Resource
    Electronic Resource
    Nitro- und Allyloxy-substituierte helicale [2.2]Metacyclophane: Synthese, Circulardichroismus und Röntgen-Kristallstrukturanalysen (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1585-1590 
    Details
    ISSN: 0009-2940
    Keywords: Charge transfer ; Circular dichroism ; Helical molecules ; [2.2]Metacyclophanes ; Structure-chiroptic relationships ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nitro- and Allyloxy-Substituted Helical [2.2]Metacyclophanes: Synthesis, Circular Dichroism and Crystal StructuresThe preparations of the title compound 3a, intraannularly nitro-functionalized, of the extraannularly substituted reference compound 3b, and of the sulfone 4 are described. Enantiomeric resolution of these helical phanes was accomplished on (+)-PTrMA and cellulose tris(3,5-dimethylphenyl)carbamate by HPLC. Racemization of the enantiomers of 3b is faster than that of the previously reported extraannularly substituted phanes. The crystal structure of 3a as well as that of the allyl ether 3d show severe distortions of the benzene rings; the CD spectrum of 3a is pointing at an intramolecular charge-transfer complex, an effect that cannot be evaluated from the CD spectrum of 3b.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240719
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