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 language | English |
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Pages (from-to) | 3763–3778 |
Journal | Organometallics |
Volume | 30 |
Issue number | 14 |
Early online date | 28 Jun 2011 |
DOIs | |
Publication status | Published - 25 Jul 2011 |