Syntheses involving co-ordinatively unsaturated cyclopentadienyl-molybdenum and -tungsten complexes. Molecular and crystal structure of [Mo·C(CF3):C(CF3)·C5H 5(CF3C2CF3) (η5-C5H5)]

Jack L. Davidson, Michael Green, F. Gordon A. Stone, Alan J. Welch

Research output: Contribution to journalArticle

Abstract

The 16-electron chloro-complexes [MCl(CF3C2CF3)25-C5H5)] (M = MO or W) react with TISC6F5 to give compounds [M(SC6F5) (CF3C2CF3]25-C 5H5)]; the related species [M(SC6F5)(CO)(PhC2Ph)(η5-C 5H5)] were similarly obtained from [MCl(CO)(PhC2Ph)(η5-C5H5)]. Cyclopentadienylthallium reacts with the compounds [MCl(CF3C2CF3)25-C5H5)] to afford insertion products [MC(CF3)C(CF3)C5H5(CF 3C2CF3)(η5-C5H 5)], the molybdenum compound being characterised by a single-crystal X-ray diffraction study. It crystallises in the centrosymmetric monoclinic space-group P21/n, with lattice parameters a = 12.904(6), b = 9.641 (3), c = 15.302(6) Å, β = 103.34(4)°. The structure was elucidated via analysis of 2 148 independent diffracted data, and refined to R 0.39, R′ 0.044.

The molybdenum compound [MoCl(CF3C2CF3)25-C5H5)] undergoes an unusual reaction with the tris-(pyrazolyl)borate anion to give a complex containing no boron but an η3-allyl group, linking two pyrazole ligands and formed by condensation of the two hexafluorobut-2-yne ligands originally co-ordinated to the metal. Buta-1,3-diene reacts with [MoCl(CF3C2CF3)25-C5H5)] to give [MoCl24-C4H65-C5H5)] and with [MoCl(CO)-(PhC2Ph)(η5-C5H5)] to yield the same compound or [MoCl(CO) (η4-C4H6)(η5-C 5H5], depending on the solvent. The tungsten compound [WCl(CO)(η4-C4H6) (η5-C5H5)] was also prepared. Reactions of bicyclo[2.2.1]-heptadiene with the compounds [MCl(CF3C2CF3)25-C5H5)] were also studied.

Original languageEnglish
Pages (from-to)287-294
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number3
DOIs
Publication statusPublished - 1977

ASJC Scopus subject areas

  • Chemistry(all)

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