Synthesis, redox chemistry, and electronic structure of the alkynyl cyclopentadienyl molybdenum complexes [Mo(C≡CR)(CO)(L2)Cp']n+ (n = 0 or 1; R = Ph or C6H 4-4-Me, L2 = Ph2PCH2CH2PPh2 or 2PMe3, Cp' = Cp or Cp*)

H.N. Roberts, N.J. Brown, R. Edge, R. Lewin, D. Collison, Paul Low, M.W. Whiteley

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Two series of bis-phosphine-substituted cyclopentadienyl molybdenum alkynyl complexes, [Mo(C≡CR)(CO)(dppe)Cp′] and trans-[Mo(C≡CR)(CO)(PMe3)2Cp′] (R = Ph or C6H4-4-Me, dppe = Ph2PCH2CH2PPh2, Cp′ = Cp or Cp*), have been prepared and structurally characterized. One-electron oxidation to the 17-electron radical cations has been investigated by cyclic voltammetry and, for selected Cp* derivatives, by spectroelectrochemical IR and UV–visible methods. Through a combination of experimental measurements (IR and EPR spectroscopy) and DFT-based calculations some important differences between the two series of complexes [Mo(C≡CR)(CO)(dppe)Cp′] and trans-[Mo(C≡CR)(CO)(PMe3)2Cp′] have been established. In particular, the change in molecular geometry leads to enhanced alkynyl character in the HOMO of [Mo(C≡CR)(CO)(dppe)Cp′] when compared with the largely metal-centered HOMO of trans-[Mo(C≡CR)(CO)(PMe3)2Cp′].
Original languageEnglish
Pages (from-to)3763–3778
JournalOrganometallics
Volume30
Issue number14
Early online date28 Jun 2011
DOIs
Publication statusPublished - 25 Jul 2011

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