Reversible insertion of alkynes into molybdenum- and tungsten-sulphur bonds

Laurence Carlton, W. A. Wan Abu Bakar, Jack L. Davidson

Research output: Contribution to journalArticle

Abstract

Reactions of the bis-hexafluorobut-2-yne complex [MoCl(CF3CCCF3)2(?5-C5H5)] with thallium salts T1SR give ?2-C,C vinyl complexes [M{?3-C(CF3)C(CF3)SR}(CF3CCCF3)(?5-C5H5)] (1), fully characterised in the cases M = Mo, R = Pri, But, but only partially so in the case M = Mo, R = 4-MeC6H4. Air oxidation of ?2-C,C vinyls 1 (M = Mo, R = 4-MeC6H4; = W, R = Pri) and the isomeric bis-alkyne derivatives [MSR(CF3CCCF3)2(?5-C5H5)] (2) (M = Mo, R = C6F5; M = W, R = 4-MeC6H4) gives cis s-alkenyl-oxo derivatives [M{C(CF3)C(CF3)SR}(O)(CF3CCCF3)(?5-C5H5)] (3). With 1 (M = Mo, R = Pri) a cis-cis ?2-butadienyl complex [Mo{?2-C(CF3)C(CF3)C(CF3)C(CF3)SPri}(O)(?5-C5H5)] 4 is obtained instead, whereas air oxidation of [WSC6F5(CF3CCCF3)2(?5-C5H5)] gives a dimeric alkyne derivative [W2(CF3CCCF3)4(O)n(?5-C5H5)2] (n = 1 or 2) (5) resulting from loss of the thiolate ligand. Reactions of s-alkenyl-oxo complexes 3 (M = Mo, R = C6F5; M = W, R = 4-MeC6H4) with tertiary phosphines L give ?2-vinyl complexes [MSR{?2-C(CF3)C(CF3)L}(CF3CCCF3)(?5-C5H5)] (M = Mo, R = C6F5, L = PEt3 or PMe2Ph; M = W, R = 4-MeC6H4, L = PEt3, PMe2Ph or PMePh2) (6) as a result of reduction of the metal MIV ? MII and thiolate migration to the metal. © 1990.

Original languageEnglish
Pages (from-to)177-193
Number of pages17
JournalJournal of Organometallic Chemistry
Volume394
Issue number1-3
Publication statusPublished - 11 Aug 1990

Fingerprint Dive into the research topics of 'Reversible insertion of alkynes into molybdenum- and tungsten-sulphur bonds'. Together they form a unique fingerprint.

  • Cite this

    Carlton, L., Wan Abu Bakar, W. A., & Davidson, J. L. (1990). Reversible insertion of alkynes into molybdenum- and tungsten-sulphur bonds. Journal of Organometallic Chemistry, 394(1-3), 177-193.