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  • Phosphanes  (2)
  • Bis[tris(1, 2-dimethoxyethan)lithium(1 +)]-1, 4-bis(trimethylsilyl)-1,1,4,4-tetrakis (pentacarbonylchrom(0))-tetraphos-2-phenat(2-)  (1)
  • 1
    ISSN: 0044-2313
    Keywords: Phosphanes ; silylphosphanes ; 1,1,3,3-tetrakis(trimethylsilyl)triphosphane ; tetracarbonyl {1,1,3,3-tetrakis(trimethylsilyl)triphosphane-1k2P1P2}chromium ; tetracarbonyl{1-lithio-1,3,3-tris(trimethylsilyl)triphosphane-1k2P1P2}chromium ; tetracarbonyl{1,3,3-tris(trimethylsilyl)triphosphane-1k2P1P2}chromium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. X. The Influence of the Formation of Complex Compounds on the Reactivity of [(Me3Si)2P]2PHWhereas [(Me3Si)2P]2PH 1 by BuLi is attacked at the PH group to give [(Me3Si)2P]2PLi 2, the related chromium carbonyl complex (Me3Si)12PIV — 2PIV(H) — 3PIII(Si—Me3)2 · Cr(CO)4 3 with BuLi yields Li(Me3Si)1PIV — 2PIV(H) — 3PIII(SiMe3)2 · Cr(CO)4 4 by cleaving a Si—P bond at the chromium substituted 1P atom. Dissolved in ether, 4 is stable for a longer time, while under comparable conditions 2 forms Li3P7 which is not obtained from 4. MeOH in 3 cleaves selectively the Me3Si groups from the complex substituted P atom yielding (Me3Si)(H)1PIV — 2PIV(H) — 3PIII(SiMe3)2 · Cr(CO)4 5 and H21PIV — 2PIV(H) — 3PIII(SiMe3)2Cr(CO)4 6. 5 and 6 seem to be stable in contrast to the uncoordinated triphosphanes which are not known.
    Notes: Während [(Me3Si)2P]2PH 1 mit LiBu unter Substitution der PH-Gruppe [(Me3Si)2P]2PLi 2 bildet, reagiert dessen Chromcarbonylkomplex (Me3Si)12PIV — 2PIV(H) — 3PIII(SiMe3)2 · Cr(CO)4 3 mit LiBu unter Spaltung einer Si—P-Bindung am komplexierten 1P-Atom zum Li(Me3Si)1PIV — 2PIV(H) — 3PIII(SiMe3)2 · Cr(CO)4 4. 4 ist in etherischer Lösung über längere Zeit beständig, während 2 unter diesen Bedingungen umgehend unter Bildung von Li3P7 weiterreagiert, das von 4 nicht gebildet wird. Mit MeOH werden in 3 selektiv die Me3Si—P-Gruppen am komplexierten 1P-Atom unter Bildung von (Me3Si)(H)1PIV — 2PIV(H) — 3PIII(SiMe3)2 · Cr(CO)4 5 und H21PIV — 2PIV(H) — 3PIII(SiMe3)2Cr(CO)4 6 gespalten. In 5 und 6 sind die im unkomplexierten Zustand bisher nicht bekannten Triphosphane offensichtlich stabilisiert.
    Additional Material: 1 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: [Li(DME)3]2{(SiMe3)[Cr(CO)5] 2 P—P = P—P[Cr(CO)5]2[(SiMe3)]} ; Bis[tris(1, 2-dimethoxyethan)lithium(1 +)]-1, 4-bis(trimethylsilyl)-1,1,4,4-tetrakis (pentacarbonylchrom(0))-tetraphos-2-phenat(2-) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII. Formation and Structure of [Li(DME)3]2{(SiMe3)[Cr(CO)5]2 P-P = P-P[Cr(CO)5]2(SiMe3)}Deep red crystals of the title compound 1 are produced in the reaction of LiP(Me3Si)2[Cr(CO)5] with 1, 2-dibromoethane in DME. The structure of 1 was derived from the investigation of the 31P-NMR spectra and confirmed by a single crystal structure determination. 1 crystallizes in the space group P1 (no. 2); a = 1307.8(5)pm, b = 1373.1(5)pm, c = 1236.1(4)pm, α = 106.22(4)°, β = 88.00(3)°, γ = 115.52(4)° and Z = 1. 1 forms a salt composed of a dianion R2R4′P42- (R = SiMe3, R′ = Cr(CO)5) and solvated Li+ cations. The zigzag shaped dianion possesses the symmetry 1-Ci. The distances d(P—P) = 202.5(1)pm and d(P—P) = 221.9(1)pm correspond to a double bond and single bonds, respectively. The distances d(Cr—P) = 251.1(1) pm and 255.3(1) pm are larger than those observed so far which might be caused by the charge distribution in the dianion.
    Notes: Bei der Umsetzung von LiP(SiMe3)2[Cr(CO)5] mit 1, 2-Dibromethan in DME entstehen die rubinroten Kristalle der Titelverbindung 1. Die Struktur von 1 folgt aus der Untersuchung der 31P-NMR-Spektren und der Einkristallstrukturbestimmung. 1 kristallisiert in der Raumgruppe P1 (Nr. 2); a = 1 307,8(5) pm. b = 1373,1(5) pm, c = 1236, 1(4) pm, α = 106,22(4)°, β = 88,00(3)°, γ = 115,52(4)° mit Z = 1. 1 bildet ein Salz aus einem Dianion R2R4′P42 (R = SiMe3, R′ = Cr(CO)5) und solvatisierten Li+-Kationen. Das gewinkelte Dianion hat die Symmetrie 1-C1. Die Abstände d(P—P) = 202,5(1) pm und (d)P—P = 221,9(1) pm entsprechen einer Doppelbindung bzw. Einfachbindungen. Die Abstände d (Cr—P) = 251,1(1) pm bzw. 255,3(1) pm sind größer als bisher beobachtete, was auf die Ladungsverteilung im Anion zurückgeführt wird.
    Additional Material: 2 Ill.
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  • 3
    ISSN: 0044-2313
    Keywords: Phosphanes ; Phosphinophosphinidene-phosphoranes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of tBu2P—P=P(Br)tBu2 with Phosphanes A Route to Variously Substituted Phosphinophosphinidene-phosphoranestBu2P—P=P(Br)tBu2 1 reacts with PR3 [R3 = Et3, tBu3, Ph3, (NMe2)3, (NEt2)3, (NEt2)2Me, Me2SiMe3] according totBu2P—P=P(Br)tBu2 + PR3 → tBu2P—P=PR3 + tBu2PBrWhile 1 decomposes above -30°C yielding tBu2PBr and the cyclophosphanes (tBu2P)3P3 and (tBu2P)4P4, there is no condensation to give any cyclophosphanes from the intermediately formed tBu2P—P in the presence of PR3. The chlorophosphanes tBu2PCl, tBuPPhCl, (Et2N)2PCl and Ph2PCl as well as (CF3)2PBr react quite analogously to the above equation yielding tBu2P—P=P(Cl)tBu2, tBu2P—P=PtBuPhCl, tBu2P—P=P(NEt2)2Cl and tBu2P—P=P(NEt2)2Br.
    Notes: tBu2P—P=P(Br)tBu2 1 reagiert mit PR3 [R3 = Et3, tBu3, Ph3, (NMe2)3, (NEt2)3, (NEt2)2Me, Me2SiMe3] nachtBu2P—P=P(Br)tBu2 + PR3 → tBu2P—P=PR3 + tBu2PBrWährend 1 oberhalb -30°C unter Bildung von tBu2PBr und der Cyclophosphane (tBu2P)3P3, (tBu2P)4P4 zerfällt, unterbleibt die Kondensation des intermediär auftretenden tBu2P—P zu den Cyclophosphanen in Anwesenheit von PR3 aufgrund der Addition des Phosphans. Die Chlorphosphane tBu2PCl, tBuPhPCl, (Et2N)2PCl und Ph2PCl sowie (CF3)2PBr reagieren weitgehend entsprechend Gl. (1) unter Bildung von tBu2P—P=PtBu2Cl, tBu2P—P=PtBuPhCl, tBu2P—P=P(NEt2)2Cl, tBu2P—P=P(NEt2)2Br.
    Additional Material: 4 Tab.
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