The synthesis and characterization of two linear trinuclear V(III) complexes are described : 1, [LV(mu-(PhO)(2)PO2)(3)V-(mu-(PhO)(2)PO2)(3)VL]PF6, and 2, LV(mu-(PhO)(2)PO2)(2)(mu-OH)V(mu-(PhO)(2)PO2)(2)(mu-OH)VL]ClO4 where L = hydridotris(pyrazolyl)borate. Compound 1 consists of two terminal V(III) ions capped by a hydridotris (pyrazolyl)berate group and each linked to a central V(III) by three (mu-O, mu-O’) diphenyl phosphate bridges. The structure of 2 is analogous but with a hydroxide bridge replacing a diphenyl phosphate in each link. X-ray crystal structural analysis of 1 and 2 gave the following parameters : 1, C98H92B2F6N16O24P7V3, P (1) over bar, a = 14.191(6) Angstrom, b = 14.338(4) Angstrom, c = 14.471(3) Angstrom, alpha = 76.41(3)degrees, beta = 71.10(3)degrees, gamma = 81.22(2)degrees, Z = 1, V = 2698.3(15) Angstrom(3); 2, C70H68B2ClN14O22P4V3, P2(1)/n, a = 13.035(5) Angstrom, b = 17.280(4) Angstrom, c = 19.343(8) Angstrom, beta = 109.18(2)degrees, Z = 2, V = 4115(2) Angstrom(3). Magnetic measurements indicate that replacement of one phosphate bridge with a hydroxide leads to a change in the sign of the coupling between the terminal and central V(III) atoms from antiferromagnetic (AF) in 1 to ferromagnetic (FM) in 2. The similarity in structure between 2 and the previously reported [L(2)V(2)(mu-(PhO)(2)PO2)(2)(mu-OH)]ClO4 allows a comparison between their magnetic properties and confirms the previously postulated idea that the crossover from AF to FM coupling comes near a bridge angle of 133 degrees.