Triadic coupling between hydride, acetylide and alkyne on the complex [WRe(η-C₅Me₅)O(CO)₄( µ-H)(CCPh)]. Crystal structures of complexes containing a substituted cyclopentadienylidene ligand or a folded metallacyclopentadienyl fragment

Abstract

The reaction of the dinuclear oxoacetylide complex [WRe(η-C₅Me₅)O(CO)₄(µ-H)(µ- CCPh)] 1 with dimethyl acetylenedicarboxylate afforded the bis(alkylidene) complex [WRe(η-C₅Me₅)O(CO)₃(µ-CHPh) {µ-C₅(CO₂Me)₄}] 2, generated by formal co-ordination of two alkynes and cleavage of a C–C bond. In contrast, treatment of 1 with an excess of di-p-tolylacetylene in refluxing toluene gave three complexes [WRe(η-C₅Me₅)O(CO)₃{CH(Ph)CC (C₆H₄Me-p)CH(µ-η²-C ₆H₃Me)}] 3, [WRe(η-C₅Me₅)O(CO)₃{µ-C ₄Ph[C₂H(C₆H₄Me-p) ₂](C₆H₄Me-p)₂ }] 4 and [WRe(η-C₅Me₅)O(CO)₃{µ-C ₄[C₂H(C₆H₄Me-p) ₂]Ph(C₆H₄Me-p)₂ }] 5. Compounds 4 and 5, which possess a folded metallacyclopentadienyl fragment, are produced by hydride migration to alkyne, giving a cis-ditolylalkenyl substituent, followed by coupling with acetylide and a second ditolylacetylene molecule. Compound 3 is probably produced by a distinct sequence, involving initial formation of a C(C₆H₄Me-p)C(C₆H₄ Me-p)CCHPh linkage, followed by orthometallation and hydrogen transfer. Single-crystal structural analyses of 2–5 have been performed and the possible reaction mechanisms leading to their isolation are presented.

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