4.5 Article

N-heterocyclic carbene complexes of Zn(II): synthesis, X-ray structures and reactivity

Journal

JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 689, Issue 12, Pages 2123-2130

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2004.03.039

Keywords

N-heterocyclic carbenes; zinc; copolymerization; ring-opening polymerization

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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(+)-alpha-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 epsilon-caprolactone. (C) 2004 Published by Elsevier B.V.

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