PRODUCTS OF THE REACTION BETWEEN COPPER(I) PHENOXIDE AND TRIPHENYLPHOSPHINE

Two phenolatocopper(I) derivatives, viz. [Cu-4(PPh(3))(4)(OPh)(4)] (1) and [Cu-2(PPh(3))(3)(OPh)(2)], (2), where Ph = C6H5, have been prepar ed by the addition of triphenylphosphine to copper (I) phenoxide, obta ined from mesitylcopper(I) and phenol. Characterisation by means of cr ystal structure determination showed 1 to be a tetramer with a cubane- type Cu4O4 core in which Cu-O distances range from 2.05(2)-2.26(2) Ang strom. Complex 2 is a mu(2)-phenoxide dimer in which one copper(I) cen tre is four-coordinated by two phenoxide and two triphenylphosphine li gands, while the other is coordinated by a single triphenylphosphine l igand and thus three-coordinated. Complex 1 crystallises as the solvat e [Cu-4(PPh(3))(4)(OPh)(4)].(C6H5CH3)(2) in the monoclinic space group P2(1)/c with a = 14.822(7), b = 23.160(4), c = 28.193(6) Angstrom, be ta = 98.64(2)degrees, V = 9569(5) Angstrom(3) at -90 degrees C and Z = 4; full-matrix least-squares refinement yielded R = 0.082 for 529 par ameters and 3931 observed reflections. [Cu-2(PPh(3))(3)(OPh)(2)] (2) c rystallises in the triclinic group P (1) over bar with a = 13.948(4), b = 16.846(2), c = 12.480(3) Angstrom, alpha = 94.92(2), beta = 110.45 (2), gamma = 95.96(2)degrees, V = 2709(2) Angstrom(3) at -120 degrees C and Z = 2; full-matrix least-squares refinement yielded R = 0.063 fo r 328 parameters and 2507 observed reflections. The effect of increasi ng the PPh(3):CuOPh ratio on the stability of the phenoxide is discuss ed in terms of the coordination geometry and consequent accessibility of the metal to small molecules.