Vanadium Hydrotris(pyrazolyl)borate Complexes of Diphenyl Phosphate. Heterometallic Complexes of the [LV{(PhO)2PO2}3 ] - Fragment

The synthesis and characterization of nine trinuclear, mixed metal complexes of the type [LV{μ-(PhO)2PO2}3]2M, where the vanadium is in the 3+ oxidation state, L = hydrotris(pyrazolyl)borate, and M = Ba(II) (1), Ca(II) (2), Mg(II) (3), Mn(II) (4), Co(II) (5), Ni(II) (6), Fe(II) (7), 2 Na(I) (8), Al(III) (9), and La(III) (10), are described. X-ray crystal structural analysis of 1, 3, and 4 gave the following parameters: 1, C92H84B2N12O24P6Cl4BaV2, C2/c, a = 26.730(5) Å, b = 15.521(3) Å, c = 27.648(6) Å, β = 100.53(3)°, Z = 4; 3, C94H80B2N14O24P6MgV2, P1̄, a = 13.410(3) Å, b = 14.179(3) Å, c = 15.694(3) Å, α = 112.22(3)°, β = 101.31(3)°, γ = 106.15(3)°, Z = 1; 4, C111H80B2N12O28P6MnV2, R3̄c, a = 18.670(3) Å, b = 18.671(3) Å, c = 61.114(12) Å, Z = 6. Magnetic measurements indicate that compounds containing an integral spin central ion display moderate antiferromagnetic coupling while those with half-integral spins give more complex behavior.