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

The synthesis and characterization of nine trinuclear, mixed metal complexes of the type [LV{&mgr;-(PhO)(2)PO(2)}(3)](2)M, 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, C(92)H(84)B(2)N(12)O(24)P(6)Cl(4)BaV(2), C2/c, a = 26.730(5) Å, b = 15.521(3) Å, c = 27.648(6) Å, beta = 100.53(3) degrees, Z = 4; 3, C(94)H(80)B(2)N(14)O(24)P(6)MgV(2), P&onemacr;, a = 13.410(3) Å, b = 14.179(3) Å, c = 15.694(3) Å, alpha = 112.22(3) degrees, beta = 101.31(3) degrees, gamma = 106.15(3) degrees, Z = 1; 4, C(111)H(80)B(2)N(12)O(28)P(6)MnV(2), R&thremacr;c, 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.

Non-Template-Centered, Closed Tetravanadium Phosphate and Phosphonate Clusters.

Tetranuclear V(III) complexes, [HB(pz)(3)](4)V(4)(&mgr;-C(6)H(5)OPO(3))(4) (I), its acetonitrile solvate (I.4CH(3)CN), and [HB(pz)(3)](4)V(4)(&mgr;-O(2)NC(6)H(4)OPO(3))(4).4C(7)H(8).H(2)O (II), and tetranuclear vanadyl complexes, (t-Bupz)(4)V(4)O(4)(&mgr;-C(6)H(5)PO(3))(4).2H(2)O (III) and (t-Bupz)(5)V(4)O(4)(&mgr;-C(6)H(5)PO(3))(4).4CH(3)CN.0.6 H(2)O (IV), have been prepared and characterized by spectroscopic, magnetic, and electrochemical methods (pz = pyrazole, t-Bupz = tert-butylpyrazole). The use of organic solvents and bulky organic groups as ancillary ligands leads to formation of neutral species instead of the anionic clusters commonly found in the hydrothermal synthesis of vanadium organophosphate/phosphonate systems. Complexes I.4CH(3)CN and IV have also been characterized by single-crystal X-ray diffraction. Crystal data: I.4CH(3)CN, triclinic, P&onemacr;, a = 15.495(3) Å, b = 17.000(3) Å, c = 17.949(4) Å, alpha = 89.17(3) degrees, beta = 86.00(3) degrees, gamma = 78.60(3) degrees, Z = 2; IV, triclinic, P&onemacr;, a = 15.541(3) Å, b = 16.340(2) Å, c = 19.069(5) Å, alpha = 83.58(2) degrees, beta = 79.67(2) degrees, gamma = 63.68(1) degrees, Z = 2. Both are closed clusters, the core structure of the first consisting of a cubane-like arrangement of metal octahedra and phosphate tetrahedra and the core structure of the second consisting of a distorted, collapsed variant of the first. Unlike other vanadium phosphate clusters, these compounds form in the absence of a central, templating agent. As such they represent the simplest form of a closed cluster in which steric forces and cluster connectivity requirements play the primary role in organizing the cluster framework.