Synthesis and structure of CpMo(CO)(dppe)H and its oxidation by Ph 3C +

Tan Yun Cheng, David J. Szalda, Jie Zhang, R. Morris Bullock

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The reaction of CpMo(CO)(dppe)Cl (dppe = Ph 2PCH 2CH 2PPh 2) with Na +[AlH 2(OCH 2CH 2OCH 3) 2] - gives the molybdenum hydride complex CpMo(CO)(dppe)H, the structure of which was determined by X-ray crystallography. Electrochemical oxidation of CpMo(CO)(dppe)H in CH 3CN is quasi-reversible, with the peak potential at -0.15 V (vs Fc/Fc +). The reaction of CpMo(CO)(dppe)H with 1 equiv of Ph 3C +BF 4 - in CD 3CN gives [CpMo(CO)(dppe)-(NCCD 3)] + as the organometallic product, along with dihydrogen and Gomberg's dimer (which is formed by dimerization of Ph 3C ). The proposed mechanism involves one-electron oxidation of CpMo(CO)(dppe)H by Ph 3C + to give the radical-cation complex [CpMo(CO)(dppe)H] •+. Proton transfer from [CpMo(CO)(dppe)H] •+ to CpMo(CO)(dppe)H, loss of dihydrogen from [CpMo(CO)(dppe)(H) 2] +, and oxidation of Cp(CO)(dppe)Mo by Ph 3C + lead to the observed products. In the presence of an amine base, the stoichiometry changes, with 2 equiv of Ph 3C + being required for each 1 equiv of CpMo(CO)(dppe)H because of deprotonation of [CpMo(CO)(dppe)H] •+ by the amine. Protonation of CpMo(CO)(dppe)H by HOTf provides the dihydride complex [CpMo(CO)(dppe)(H) 2] +OTf -, which loses dihydrogen to generate CpMo(CO)(dppe)(OTf).

Original languageEnglish
Pages (from-to)4712-4720
Number of pages9
JournalInorganic Chemistry
Volume45
Issue number12
DOIs
Publication statusPublished - Jun 12 2006

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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