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Reactivity of the Inversely Polarised Arsaalkenes R–As=C(NMe2)2 {R = [(η5-C5Me5)(CO)2Fe], tBuC(O)} Towards Vinylidene Complexes [η5-(C5H5)(CO)(NO)W=C=C(H)R] (R = Ph, tBu)

✍ Scribed by Lothar Weber; Philipp Bayer; Gabriel Noveski; Hans-Georg Stammler; Beate Neumann

Publisher
John Wiley and Sons
Year
2006
Tongue
English
Weight
177 KB
Volume
2006
Category
Article
ISSN
1434-1948

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✦ Synopsis

Abstract

The reaction of the vinylidene complexes [(C~5~H~5~)(CO)(NO)W=C=C(H)R] (10a: R = __t__Bu; 10b: R = Ph) with the arsaalkene __t__BuC(O)–As=C(NMe~2~)~2~ (11) afforded the novel η^2^‐1‐arsaallene complexes [η^2^‐{__t__BuC(O)–As=C=C(H)R}W(CO)(NO)C~5~H~5~] (13: R = __t__Bu; 15: R = Ph). Similarly, treatment of 10a with the ferrioarsaalkene [(C~5~Me~5~)(CO)~2~Fe–As=C(NMe~2~)~2~] (12) led to the formation of [η^2^‐{[(C~5~Me~5~)(CO)~2~Fe]–As=C=C(H)__t__Bu}W(CO)(NO)(C~5~H~5~)] (14), whereas combination of 12 and 10b yielded the carbene complex [(C~5~H~5~)(CO)(NO)W=C(NMe~2~)C(Ph)=C(H)NMe~2~] (16) in high yield instead of the anticipated arsaallene complex. The novel compounds 13, 14, 15 and 16 were characterised by elemental analyses and by means of spectroscopy (IR, ^1^H, ^13^C NMR). Moreover, the molecular structures of 14 and 15 were elucidated by X‐ray diffraction analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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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