Abstract
Copper(II) acetate reacts with triphenylphosphine, in ethanol solution, in a manner depending on the concentration of Cu(O2CMe)2, the molar ratio of PPh3 to CuII, and temperature, to form the copper(I) complex [Cu(O2CMe)(PPh3)n](n= 2 or 3), the copper(II) complex [Cu2(O2CMe)4(PPh3)2], and the mixed-valence copper(I,II) complex [Cu4(O2CMe)6(PPh3)4]. The pale blue-green complex [Cu4(O2CMe)6(PPh3)4] has been characterized by microanalysis, electronic, i.r., and e.s.r. spectra, and magnetic susceptibility measurements. The crystal and molecular structure of [Cu4(O2CMe)6(PPh3)4] has been determined from X-ray diffractometer data by the heavy-atom method and refined by full-matrix least-squares methods to R= 0.0565 for 2 227 reflections. Crystals are triclinic, space group P, with a= 10.898(8), b= 12.850(4), c= 19.877(8)A, α= 121.03(2), β= 90.14(5), γ= 117.98(4)°, and Z= 1. The crystal structure comprises centrosymmetrical molecules of [Cu4(O2CMe)6(PPh3)4]. Each molecule consists of a Cu2(O2CMe)4 dimeric unit in the axial positions to which two molecular Cu(O2CMe)(PPh3)2 ligands are co-ordinated through the oxygen atom of each acetate group.
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