Synthesis and reactivity of cyclopentadienyl chloro, imido and alkylidene tungsten (VI) complexes
Identifiers
Permanent link (URI): http://hdl.handle.net/10017/4249DOI: 10.1016/S0022-328X(98)00639-1
ISSN: 0022-328X
Publisher
Elsevier
Date
1998Bibliographic citation
Journal of Organometallic Chemistry, 1998, v.564, n.1-2, p.277-281
Keywords
Alkyl
Alkylidene
Cyclopentadienyl
Imido
Tungsten
Project
PB92-0178-C (Ministerio de Educación y CulturaI
UA 040/96 (Universidad de Alcalá)
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Publisher's version
http://dx.doi.org/10.1016/S0022-328X(98)00639-1Rights
© Elsevier, 1998
Access rights
info:eu-repo/semantics/openAccess
Abstract
This paper describes the synthesis and characterization of alkylidene pentamethylcyclopentadienyl imido tungsten(VI) complexes via α-hydrogen abstraction processes from suitable alkyl derivatives. Reaction of WCp*Cl4 with one equivalent of NH2R (R=tBu, 2,6-Me2–C6H3), two equivalents of NEt3 and subsequent oxidation with PCl5 affords the pentamethylcyclopentadienyl imido tungsten derivatives, WCp*(NtBu)Cl32 and WCp*(N-2,6-(Me2)–C6H3)Cl34. Alkylation of complexes 2 and 4 with 1.5 equivalents of ZnMe2 under appropriate conditions yields the trimethyl derivatives WCp*(NtBu)Me35 and WCp*(N-2,6-(Me2)–C6H3)Me3 6. Exposure of complex 6 to sun-light leads to the formation of WCp*(N-2,6-(Me2)–C6H3)(CH2)Me 7 through a α-hydrogen abstraction process. Analogously, complex 2 reacts with 1.5 equivalents of Mg(CH2Ph)-(thf)2 or three equivalents of LiCH2SiMe3 to give the alkylidene complexes, WCp*(NtBu)(CHPh)(CH2Ph) 8 and WCp*(NtBu)(CHSiMe3)Cl 9, through a spontaneous α-hydrogen abstraction process in these cases.
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