Nature of previously reported thermally unstable products derived from the reaction of [Co2(CO)8] with PhSSPh, EtSSEt or PhSeSePh and of the reactions of these products with alkynes or isocyanides

John E. Davies, Martin J. Mays, Paul R. Raithby, Vallipuram Sarveswaran, Gregory P. Shields

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10 Citations (Scopus)

Abstract

Thermally unstable red complexes previously isolated from the reaction of [Co2(CO)8] with REER (E = S, R = Ph or Et; E = Se, R = Ph) and assigned the structure [Co33-ER)(CO)9] have been reformulated as the trinuclear complexes [Co33-E)R(CO)8] (E = S, R = Ph la or Et 1b; E = Se, R = Ph 1c) on the basis of their spectroscopic properties and the nature of their reactions with alkynes and isocyanides. Thus the complexes [Co33-E)R(CO)8] 1a-1c react with PhC≡CH to give [Co33-E){PhCCHC(O)R}(CO)7] 2a-2c respectively (E = S, R = Ph 2a or Et 2b; E = Se, R = Ph 2c). It is proposed that 2a-2c are formed via migration of the R group in 1a-1c from the metal to a carbonyl carbon atom to give an acyl group. Subsequent insertion of PhC≡CH into the metal-acyl group bond is followed by co-ordination of the acyl oxygen to give a five-membered metallacyclic ring. The reaction of ButN≡C with 1a-1c gave the complexes [Co33-E)(μ-ButN=CR)(CO)7] 3a-3c respectively (E = S, R = Ph 3a or Et 3b; E = Se, R = Ph 3c) and a similar reaction pathway is proposed. The structures of complexes 2a and 3a have been determined by single-crystal X-ray diffraction studies.

Original languageEnglish
Pages (from-to)775-779
Number of pages5
JournalJournal of the Chemical Society - Dalton Transactions
Issue number5
DOIs
Publication statusPublished - 7 Mar 1998

ASJC Scopus subject areas

  • Chemistry(all)

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