title: Synthesis of (arylimido)vanadium complexes and their application for oxidative coupling reactions of silyl enol ether derivatives.
abstract: (Arylimido)vanadium(v) complexes, V(NAr)(OEt)Cl(2) [Ar = C(6)H(5), p-BrC(6)H(4), p-(MeO)C(6)H(4)] or V(NAr)Cl(3) [Ar = o-BrC(6)H(4), o-(MeO)C(6)H(4)] were synthesized by the reaction of VO(OEt)Cl(2) or VOCl(3), respectively, with the corresponding aryl isocyanates. X-Ray crystal structure determination for V(NAr)(OEt)Cl(2) (Ar = C(6)H(5) and p-BrC(6)H(4)) elucidates the alkoxido-bridged dimeric building blocks [V(NAr)(OEt)Cl(2)](2), wherein the substituent on the benzene ring was found to affect the character of the imido nitrogen. The (51)V NMR spectroscopic measurements indicated that the electronic state of the vanadium metal centre depends on the ligands connecting to the vanadium and the substituents on the benzene ring. The selective oxidative cross-coupling reaction of silyl ketene acetal with silyl enol ether was achieved using V(Np-BrC(6)H(4))Cl(3) or V(No-BrC(6)H(4))Cl(3).
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamada-oka, Suita, Osaka 565-0871Japan.
authors.forename: Masafumi
authors.initials: M
authors.lastname: Nishina
authors.forename: Toshiyuki
authors.initials: T
authors.lastname: Moriuchi
authors.forename: Toshikazu
authors.initials: T
authors.lastname: Hirao