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Syntheses, Reactivity, and X-ray Structure Analyses of the Dimeric Pentaphosphides [(tBu3Si)3P5M2]2 (M = Na, Ag) and the Bicyclo[2.1.0]pentaphosphane (tBu3Si)3P5

✍ Scribed by Hans-Wolfram Lerner; Günter Margraf; Linda Kaufmann; Jan W. Bats; Michael Bolte; Matthias Wagner

Publisher
John Wiley and Sons
Year
2005
Tongue
English
Weight
201 KB
Volume
2005
Category
Article
ISSN
1434-1948

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✦ Synopsis

Abstract

The sodium pentaphosphide dimer [(__t__Bu~3~Si)~3~P~5~Na~2~(THF)]~2~ has been synthesized in high yield from the reaction of four equivalents of the sodium silanide __t__Bu~3~SiNa with P~4~. X‐ray quality crystals of the sodium pentaphosphide dimer [(__t__Bu~3~Si)~3~P~5~Na~2~(THF)]~2~ (monoclinic, __P__2~1~/n) were grown from benzene. The sodium pentaphosphide (__t__Bu~3~Si)~3~P~5~Na~2~ can be oxidized with one equivalent of TCNE to give the bicyclo[2.1.0]pentaphosphane (__t__Bu~3~Si)~3~P~5~; it also reacts with AgOCN to give the silver pentaphosphide [(__t__Bu~3~Si)~3~P~5~Ag~2~]~2~ (monoclinic, __P__2~1~/n). Crystals of the pentaphosphane (__t__Bu~3~Si)~3~P~5~ (monoclinic, __P__2~1~/c) suitable for X‐ray diffraction were obtained from hexane at –25 °C. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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## Abstract Reaction of [(η^5^‐C~5~H~5~)(CO)~2~M=P=C(SiMe~3~)~2~] [where M = Mo (2), W (5)] with the phosphaalkene __t__BuP=C(NMe~2~)~2~ (1a) afforded the η^3^‐1,2‐diphosphaallyl complexes [(η^5^‐C~5~H~5~)(CO)~2~M{η^3^‐__t__BuPPC(SiMe~3~)~2~}], [where M = Mo (3a); M = W (6)]. Similarly, 2 and CyP=C