Synthesis and Structure of the First η3-1,2-Diphosphaallyl Complexes [(η5-C5H5)(CO)2M{η3-RPPC(SiMe3)2}] (M = Mo, R = tBu, Cy; M = W, R = tBu) from [(η5-C5H5)(CO)2M=P=C(SiMe3)2] (M = Mo, W) and Inversely Polarized Phosphaalkenes RP=C(NMe2)2 (R = tBu, Cy)

✍ Scribed by Lothar Weber; Gabriel Noveski; Ulrich Lassahn; Hans-Georg Stammler; Beate Neumann

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 162 KB
• Volume: 2005
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200400995

✦ Synopsis

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(NMe~2~)~2~ (1b; where Cy = cyclohexyl) gave rise to the formation of [(η^5^‐C~5~H~5~)(CO)~2~Mo{CyPPC(SiMe~3~)~2~}] (3b) by a phosphinidene transfer process. Small amounts of [{η^5^‐C~5~H~5~)(CO)~2~Mo}~2~{η^2^:η^2^‐Cy~3~P~5~}] (4) were formed as a minor product. However, treatment of 2 and 5 with HP=C(NMe~2~)~2~ (1c) yielded the complexes [(η^5^‐C~5~H~5~)(CO)~2~M{η^2^‐(Me~3~Si)~2~CH–P=P–C(NMe~2~)~2~}] [where M = Mo (9), W (10)]. The novel compounds 3a, 3b, 9 and 10 were characterized by means of spectroscopy (IR, ^1^H, ^13^C{^1^H}, ^31^P{^1^H} NMR, MS). Moreover, the molecular structures of 3a, 3b, 4, 6 and 10 were determined by X‐ray diffraction analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)