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DOI: 10.1039/A700229G (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2177-2182

Synthesis and structure of bimetallic complexes with σ,π-bridged monocarbene ligands[hair space]

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Yvette M. Terblans and Simon Lotz

Abstract

The Fischer method was employed to synthesize bimetallic monocarbene complexes from lithiated [Cr(SC4H4)(CO)3] and metal hexacarbonyls. In addition to the formation of [M{C[η5-C4H3SCr(CO)3 ]OEt}(CO)5] (M = Cr 1 or W 2) the complexes [M{C[η5-C4H3SCr(CO)3 ]O(CH2)4OEt}(CO)5] (M = Cr 3 or W 4), were also obtained. The formation of 3 and 4 is ascribed to the activation of tetrahydrofuran (thf) by a σ,π-co-ordinated acyl metalate, which triggers the cleavage of the thf ring and leads to its inclusion into the alkoxy substituent of the resulting carbene moiety. In polar solvents the Cr(CO)3 fragments are displaced to give known pentacarbonyl[ethoxy(thienyl)carbene] complexes and the new mononuclear carbene complexes [M{C(C4H3S)O(CH2)4OEt }(CO)5] (M = Cr 5 or W 6). The analogous benzo[b]thienyl carbene complex [Cr{C[η6-C8H5SCr(CO)3 ]OEt}(CO)5] 7 was prepared similarly, but did not afford the thf-inserted product and the corresponding conversion into the mononuclear carbene complex [Cr{C(C8H5S)OEt}(CO)5] 8, was much slower.

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