Electrochemical Generation of Sulfur-Ligated Molybdenum(II) and Molybdenum(III) Substrate Binding Sites. Preparation and Crystal Structures of [MoCl(S2CNEt2)2(Ph2PCH2CH2PPh2)][BF4] and [MoCl(S2CNEt2)2(PPh2Me)2][PF6] and the Mechanism of Their Electrochemical Reduction

Jonathan R. Dilworth, Bryan D. Neaves, Christopher J. Pickett, Joseph Chatt, Jon A. Zubieta

Research output: Contribution to journalArticle

23 Scopus citations

Abstract

The complexes [MoX(S2CNR2)2P2] [Y] or [MoX2(S2CNR2)2P] (R2 = Me2, Et2, or (CH2)5; X = CI or Br; Y = Cl, PF6, BF4, or BPh4; P = 1/2 Ph2PCH2CH2PPh2, PPh2Me, PMe2Ph, or PEt2Ph) are prepared from [MoOX2(S2CNR2)2] and P. The crystal and molecular structures of [MoCl(S2CNEt2)2(dppe)] [BF4] (I) and [MoCl(S2CNEt2)2(PPh2Me)2] [PF6] (VII) have been determined by single-crystal X-ray diffraction methods. Crystal data for complex I: space group P1, a = 11.422 (7) Å, b = 11.902 (9) Å, c = 16.900 (8) Å, α = 104.64 (l)°,β = 101.65 (2)°, γ = 103.34 (1)°, V= 2078.60 Å3, Z = 2, R = 6.8% from 5429 reflections. Crystal data for complex VII: space group P2'2'2’, a = 9.132 (7) Å, b = 17.028 (7)Å, c = 28.084 (7) Å,V= 4367.42 Å3, Z = 4, R = 9.8% from 2783 reflections. Both complexes have distorted pentagonal-bipyramidal geometries. Chemical or electrochemical reduction of [MoCl(S2CNR2)2(dppe)]+ under CO gives [Mo(CO)(S2CNR2)2(dppe)], whereas under N2 or Ar dimeric [{Mo(S2CNR2)2(dppe)}2]2+ is formed. The redox chemistry of these species and other intermediates has been studied by a range of electrochemical techniques, and reduction mechanisms are proposed, together with the implications for the binding of small molecules to the reductively generated site.

Original languageEnglish (US)
Pages (from-to)3524-3529
Number of pages6
JournalInorganic Chemistry
Volume22
Issue number24
DOIs
StatePublished - Nov 1983
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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