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DOI: 10.1039/A705621D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 4671-4676

Selective C–C bond formation at diiron µ-aminocarbyne complexes[hair space]†

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Vincenzo G. Albano, Luigi Busetto, Chiara Camiletti, Carlo Castellari, Magda Monari and Valerio Zanotti

Abstract

The reactions of [Fe2{µ-CN(Me)R}(µ-CO)(CO)2(Cp)2]SO3CF3 (Cp = η-C5H5, R = Me 2a or CH2Ph 2b) with a variety of carbon nucleophiles result in C–C bond formation at different sites of the molecules depending on the nature of the carbanions: (i) R′Li (R′ = Me, Bun or Ph) and R′MgCl (R′ = Me, CH2Ph or Pri) added at the Cp ligand giving η4-cyclopentadiene complexes [Fe2{µ-CN(Me)R}(µ-CO)(CO)2(η4-C5H5R′)(Cp)] 3; (ii) Li2Cu(CN)R′2 (R′ = Me or Bun) and LiC[triple bond, length half m-dash]CR′ (R′ = Ph or p-tolyl) afforded the stable acyl complexes [Fe2{µ-CN(Me)R}(µ-CO)(CO){C(O)R′}(Cp)2] 4 and [Fe2{µ-CN(Me)R}(µ-CO)(CO){C(O)C[triple bond, length half m-dash]CR′}(Cp)2] 5, respectively. With R ≠ Me the NMR spectra of type 3–5 derivatives show the presence of two isomers arising from the double-bond character of the µ-C[double bond, length half m-dash]N group ascertained from the crystal structure of [Fe2(µ-CNMe2)(µ-CO)(CO){C(O)Bun}(Cp)2] 4b. The structural study reveals the presence of interligand interactions involving the acyl oxygen and the µ-C[double bond, length half m-dash]NMe2 moiety which is also in accord with an extended-Hückel calculation of the charge distribution.

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