Crystal Structures of Cobalt(III)-Methyldiphenylphosphine Complexes. Co(III)-P Bond Lengths and Their Cleavages

Article abstract of DOI:10.1246/bcsj.68.883

The crystal structures of trans-PF6 (acac=2,4-pentanedionate ion) (1), trans-ClO4 (2), and trans(P,P)- (3) were determined by the X-ray diffraction method.Complex 1 crystallizes in the monoclinic, space group P2/n, with two molecules in a unit cell of dimensions a = 17.151(2), b = 10.347(2), c = 10.966(2) Angstroem, β = 107.84(1) deg, V = 1857.6(6) Angstroem³.Complex 2 crystallizes in the monoclinic, space group P2₁/c, with four molecules in a unit cell of dimensions a = 10.161(3), b = 17.291(5), c = 14.938(3) Angstroem, β = 91.76(2) deg, V = 2623(1) Angstroem³.Complex 3 crystallizes in the monoclinic, space group C2/c, with four molecules in a unit cell of dimensions a = 21.628(1), b = 8.974(1), c = 16.203(1) Angstroem, β = 106.396(2) deg, V = 3012.9(1) Angstroem³.The Co-P bond length for complex 1, 2.329(1) Angstroem, is significantly longer than those for complexes 2 (2.213(1) Angstroem) and 3 (2.2698(4) Angstroem).These lengths are discussed with the hydrolytic properties.