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N-heterocyclic carbene complexes of Zn(II): synthesis, X-ray structures and reactivity
Authors:Dongren Wang  Michael R. Buchmeiser
Affiliation:a Institut für Analytische Chemie und Radiochemie, Leopold-Franzens-Universität Innsbruck, Innrain 52 a, A-6020 Innsbruck, Austria
b Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 52 a, A-6020 Innsbruck, Austria
Abstract:The synthesis of six novel zinc (II) mono(N-heterocyclic carbene) complexes is described. 1,3-Bis(mesityl)-imidazol-2-ylidene was reacted with the zinc salts ZnX2 (X=Cl, CH3COO, PhCOO, and PhCH2COO) to yield the corresponding monomeric Zn-NHC complex ZnCl2(NHC)(THF) (1) and dimeric [Zn(OOCCH3)2(NHC)]2 (2), [Zn(OOCPh)2(NHC)]2 (3), [Zn(OOCCH2Ph)2(NHC)]2 (4) (NHC=1,3-bis(mesityl)-imidazol-2-ylidene). Reaction of 1 with 2 equivalents of silver trifluoromethanesulfonate yielded monomeric Zn(O3SCF3)2(NHC)(THF) (5), reaction of 1 with sodium {[R(+)-α-2-(1-phenyl-ethylimino)-methyl]-phenolate} yielded monomeric ZnCl(OC6H4-2-CHN(CHPhCH3)(NHC) (6). Compounds 1, 4-6 were structurally characterized by X-ray analysis. Selected compounds were investigated for their activity in the copolymerization of carbon dioxide with cyclohexene oxide as well as in the ring-opening polymerization of cyclohexene oxide and ε-caprolactone.
Keywords:N-heterocyclic carbenes   Zinc   Copolymerization   Ring-opening polymerization
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