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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 67-69 
    ISSN: 0009-2940
    Keywords: Diphosphabicyclobutanes / Valence isomerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DiphosphabicyclobutanesTwo isomeric diphosphabicyclobutanes (5,11) are obtained by treatment of the phosphaalkenes X-P = C(Ph)Tms (1a) and X - P = CTms2 (1b) (X = halogen Tms = trimethylsilyl) with 2, Mg, or Na. Both syntheses proceed by coupling of two phosphaalkene units affording, however, two different diphospha-butadiene intermediates. 4 and 10 readily undergo isomerization reactions to form the diphosphabicyclobutanes. Irradiation of the phosphaalkenes Cp* - P = C(Ph)Tms (12a) and Cp* - P = CTms2 (12b) (Cp* = C5Me5) gives rise to a different reaction pathway. Dimerization of 12a, followed by homolytic cleavage of the Cp* - phosphorus bond and intramolecular recombination produces the butterfly compound 5, whereas homolytic cleavage of the Cp* - element bond in 12 b, followed by rearrangement and intermolecular recombination, affords the diphosphabicyclobutane 11.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 13-16 
    ISSN: 0009-2940
    Keywords: Diphosphines, tetrakis(diisopropylamino) ; Phosphinous anhydrides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Structure of Bis[bis(diisopropylamino)phosphino]chalcogenidesPhosphorodiamidous chalcogeno-anhydrides [(R2N)2P]2X (R = Me2CH; X = S, Se, Te) (2a-c) have been obtained by insertion of elemental sulfur, selenium, or tellurium into the P-P bond of the corresponding diphosphane (1). The structure of 2a and 2c has been confirmed by an X-ray diffraction.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 93-96 
    ISSN: 0009-2940
    Keywords: Diazaphosphiridine oxides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis, Structure, and Isomerization of Diazaphosphiridine OxidesHerrn Professor Joseph Grobe zum 60. Geburtstag gewidmet.The 1,2-Bis(alkyl)iminophosphane, Et3C  -  P=N  -  tBu (1), reacts with nitroso compounds, RNO (R=tBu, Ph), to form the diazaphosphiridine oxides, Et3C  -  YYP(=O)  -  NtBu  -  NYYR, 4a, b. While 4a (R=tBu) is thermally stable, 4b (R=Ph) isomerizes with formation of the benzodiazaphosphole oxide Et3C  -  YYP(= O)  -  NH  -  C6H4  -  NYYtBu (5). The corresponding phospholimine Et3C  -  YYP(=NtBu)  -  NH  -  C6H4  -  NYYtBu (7) has been obtained from 1 and azobenzene. The three-membered phosphorus heterocycle 4a has been characterized by X-ray structure analysis, which reveales some remarkable features.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0009-2940
    Keywords: Phosphoranes, bis(methylene), isomerization of ; λ3-Phosphiranes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(methylene)phosphoranes - Synthesis, Spectroscopic Investigations and Thermal Isomerizations to λ3-PhosphiranesA great number of differently substituted bis(methylene)phosphoranes 10 [R - P{ = C(SiMe3)2}2] are obtained by nucleophilic substitution from bis[bis(trimethylsilyl)methylene]-chlorophosphorane (8). The reactions of dichlorophosphanes 1 and methylenephosphanes 3 with lithium carbenoides 2 furnish the mixed derivatives 6 [R - P( = CR1R2)( = CR3R4)] and 7 [R - P( = C(SiMe3)2( = CR3R4)]. Among these the reaction of the sterically less hindered methylenephosphanes 3c, d [R2N - P = C(H)SiMe3, R = Et, iPr] with an excess of the lithium carbenoide 2b results in the formation of the σ4λ5-phosphiranes 11a, b {R2N - P[ = C(H)SiMe3]2}. The sterically highly demanding substituents in 10a - o render great thermal stability, while the mixed bis(methylene)phosphoranes 6, 7 rearrange to the corresponding σ4λ5-phosphiranes 15a-o. Investigations performed between 30 and 180°C reveal that all bis(methylene)phosphoranes, with the exception of 6c, k - m and 7e, can be isomerized. - The phosphino-substituted bis(methylene)phosphoranes 10k, 1 show different reactivity. Light-and thermally induced cleavage of the P - P bond, and dimerization of the corresponding fragments result in the formation of 14 and the diphosphanes 13a, b. The bis(methylene)phosphoranes 10a-o are investigated by UV and NMR spectroscopy.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 645-648 
    ISSN: 0009-2940
    Keywords: Diphosphiranes, molecular structure of ; 1,2-Diphospha-2-propene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis, Structure, and Reactivity of DiphosphiranesThe 1,1-diamino-1,2-diphospha-2-propen (2,6-Me2C5H8N)2P - P=C(SiMe3)2 (3) is obtained by treatment of bis(2,6-dimethyl-piperidino)(trimethylsilyl)phosphane (1) with [bis(trimethylsilyl)methylene]chlorophosphane (2). Compound 3 readily undergoes thermally isomerization to the diphosphirane 2,6- Nucleophilic substitution of the P1-chloro function of 1-chloro-2-(diisopropylamino)1-3,3-bis(trimethylsilyl)diphosphirane (6) leads to alkyl, amino, phosphanyl, and arsanyl derivatives 7a - d. The corresponding hydrogen derivative 7e is formed by reduction of 6 with tri-n1-butylstannane. The molecular structure of 7c as well as the NMR data of the diphosphiranes are discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 649-655 
    ISSN: 0009-2940
    Keywords: λ51-Phosphirenes, imino- ; λ51-Phosphaspiro[2.2]pentanes, imino ; Imines ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Structure of Phosphirene Imines and Iminophosphaspiro[2.2]pentanesThe reaction of the iminophosphanes R1P=NR2=[1, R2=2,4,6-tBu3C6H2;R1=Me (a) Et (b), PhCH=CH (c), Cl (d); R2=tBu, R1=Et3C (e)] with the alkynes R3C ≡ CR4 [2, R3=R4=Ph (a), CO2Me (b)] affords the corresponding phosphirene imines 3a - g. A [2 + 1] cycloadduct 3h is also formed in the reaction of the alkyne 2c (R3=H, R4=Ph) with 1d, while in the case of 1b the 1,2-addition product 4 is obtained. As demonstrated by the [2 + 1] cycloaddition reaction of the P1-alkylated iminophosphanes 1a, b with methylene-cyclopropanes 5a, b, the formation of the iminophosphaspiro[2.2]pentanes 6a, b is observed. The structures of the P/C heterocycles 3a, b and 6b have been determined by NMR spectroscopy and X-ray analysis.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 2397-2401 
    ISSN: 0009-2940
    Keywords: [Amino(imino)phosphane]gallium trichloride adduct ; 1,3-Diaza-2λ2-phosphonia-4λ4-gallatacyclobutanes ; Nickel tricarbonyl complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Diaza-2λ2-phosphonia-4λ4-gallatacyclobutanesReaction of amino(imino)phosphanes 1a-c with gallium trichloride results in the formation of 1,3-diaza-2λ2-phosphonia-4λ4-gallatacyclobutanes 3a, b with elimination of chlorotrimethylsilane (1a) or tert-butyl chloride (1b, c). The intermediately formed amino(imino)phosphane/Lewis acid adducts R(Me3Si)NPN(GaCl3)R′ (2, R,R′ = tBu, Me3Si) can be isolated in the case of compound 2a (R = R′ = SiMe3). A diazaphosphasilacyclobutane - gallium trichloride adduct 4 is formed in a side reaction by isomerization of 2a. Reaction of compound 3b with Ni(CO)4 gives the corresponding transition metal complex 5. The NMR data and X-ray structures of compounds 2a, 4, and 5 are reported.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1973-1976 
    ISSN: 0009-2940
    Keywords: 2-Phosphonioallene ligands ; Metallobis(methylene)phosphoranes ; Nickel complexes ; Platinum complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Structure of 2-Phosphonioallene ComplexesThe reaction of the chlorobis(methylene)phosphorane 1 with reactive olefin complexes of nickel and platinium affords the 2-phosphonioallene complexes 4b and 6a,b. The structure of this new class of three-electron donor ligands, involving a lowcoordinated phosphorus (V) cation, has been elucidated by NMR spectroscopy and a single-crystal X-ray study of 6a. The reaction proceeds via a metallobis(methylene)phosphorane intermediate, which could be isolated in the case of the (Et3P)2Pt complex 3a.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 321-330 
    ISSN: 0009-2940
    Keywords: Phosphanes, (Z)-amino(imino)- ; 1,3,5-Triaza-2,4-diphospha-1,4-pentadienes, transition metal complexes of, dynamic behavior of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Knowledge of the 1,3,5-Triaza-2,4-diphospha-1,4-pentadienesHerrn Professor Heinrich Puff zum 70. Geburtstag gewidmetNucleophilic substitution reactions of the chloro(arylimino)-phosphane 1 yield the NH-functional amino(imino)phosphanes Mes*NPNHR (R = Mes, Ad, CPh3) 2d - f. Upon further reaction with 1 they are converted into the 1,3,5-triaza-2,4-diphospha-1,4-pentadienes Mes*NPN(R)PNMes* (R = Mes, Ad) 4d, e and Mes*NPN(Mes*)PNCPh3 5. According to crystal structure determinations all compounds 4a, d, e, 5 exhibit S conformation in the solid state. In addition to the “exo-endo” arrangement of the substituents (4a, 5) in the case of 4d, e the “endo-endo” conformation is observed for the first time. In solution, 4d, e and 5 are subject to dynamic rearrangements, whose mechanism is proven by NMR studies of partially 15N-enriched samples. The reaction of 4a with NorM(CO)4 (M = Cr, Mo) or Ni(CO)4 yields the metallaazadiphosphetidine complexes 6a - c Mes*NPN(tBu)PNMes*M(CO)n [M(CO)n = Cr(CO)4, Mo(CO)4, Ni(CO)2]. The crystal structure of 6a (“exo-endo-W”) is described.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0009-2940
    Keywords: 1,3-Diaza-2-phosphaallyllithium ; Calculations, ab initio ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monomer and Dimer 1,3-Diaza-2-phosphaallyllithium Complexes: Structures and Ambident Reactivity*Metallation of the NH-functional amino(imino)phosphanes Mes*NPNHR (R = CPh3, Ad, tBu) 1a-c yields the 1,3-diaza-2-phosphaallyllithium compounds 2a-c. The crystal structure shows an ether-stabilized monomer of 2a and a solvent-free dimer with an eight-membered ring in the case of 2b, c. The reaction of 2b with chlorodiphenylphosphane yields, dependent on the reaction conditions, (phosphanylamino)iminophosphane 3 or bis(imino)phosphanylphosphorane 4. The structural and reactivity is discussed on the basis of ab initio calculations.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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