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

Abstract

Abstract The crystal structures of trans-[Co(acac)2(PMePh2)2]PF6 (acac = 2,4-pentanedionate ion) (1), trans-[Co(acac)2(H2O)(PMePh2)]ClO4 (2), and trans(P,P)-[Co(acac)(CN)2(PMePh2)2] (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 = 10.996(2) Å, β = 107.84(1)°, V = 1857.6(6) Å3. 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) Å, β = 91.76(2)°, V = 2623(1) Å3. 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) Å, β = 106.396(2)°, V = 3012.9(1) Å3. The Co–P bond length for complex 1, 2.329(1) Å, is significantly longer than those for complexes 2 (2.213(1) Å) and 3 (2.2698(4) Å). These lengths are discussed with the hydrolytic properties.