Cu2(o-Ph2PC6H4C(O)CHC(O)C(CH3)3)2: Synthesis, structure, and ligand oxygenation to a mixed-valence Cu(I)-Cu(II) complex

Debra A. Wrobleski, Thomas B. Rauchfuss, Arnold L. Rheingold, Keith A. Lewis

Research output: Contribution to journalArticlepeer-review

Abstract

The synthesis of (o-(diphenylphosphino)benzoyl)pinacolone (HacacP) is described. The complexes M2(acacP)2 (M = Cu, Ag) were synthesized from the reaction of HacacP, NEt3, and Cu(CH3CN)4ClO4 or AgClO4. Treatment of a CH2Cl2 solution of Cu2(acacP)2 (1) with molecular oxygen gave Cu2(acacP)2(μ-o-O2CC6H 4P(O)Ph2) (2), which can also be prepared by treatment of 1 with Cu(o-Ph2P(O)C6H4CO2)2 and HacacP. After demetalation the organic products of the oxygenation were found to consist of equal amounts of o-Ph2P(O)C6H4CO2H and t-BuCO2H, which were derived from acacP-. The crystal structure and molecular geometry of Cu2(acacP)2(o-O2CC6H 4P(O)Ph2) has been determined by X-ray diffraction: P1, a = 13.592 (4) Å, b = 14.913 (5) Å, c = 18.501 (5) Å, α = 85.78 (3)°, β = 86.19 (2)°, γ = 72.61 (2)°, Z = 2, μ = 7.17 cm-1 (Mo Kα). The crystal structure and molecular geometry of [Cu(acacP(O))(OCH3)]2·2CH3OH have been determined by X-ray diffraction: P21/n, a = 9.750 (2) Å, b = 16.399 (3) Å, c = 16.698 (4) Å, β = 97.25 (2)°, Z = 2, μ = 9.17 cm-1 (Mo Kα).

Original languageEnglish (US)
Pages (from-to)3124-3129
Number of pages6
JournalInorganic Chemistry
Volume23
Issue number20
DOIs
StatePublished - Jan 1984

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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