Novel vanadyl (VO2+) chloro and hydroxo complexes with the hindered Tp(Pri2) (hydrotris(3,5-diisopropyl-1-pyrazolyl)borate) and Tp(Me2) (hydrotris(3,5-dimethylpyrazolyl-1-pyrazolyl)borate) ligands were prepared and structurally characterized successfully. Ligand displacement of VOCl2(MeCN)(2)(H2O) by Tp(R) afforded a series of octahedral chloro complexes, Tp(R)V(O)(Cl)(X) (1: R = Pr-2(i), X = Pz(Pri2)H; 2: R = Pri(2), X = py; 6: R = Me-2, X = NCMe). Hydrolysis of the obtained chloro complexes yielded the corresponding hydroxo complexes 4, 5, and 7, but their structures were very unique and different from that of the previously reported dinuclear VO2+ bis(mu-hydroxo) complex with the less hindered Tp(H2) (hydrotris(1-pyrazolyl)borate) ligand. For the Tp(Pri2) complexes, the octahedral hydroxo-aqua complex, Tp(Pri2)V(O)(OH)(OH2) (4), and the trinuclear bis(mu u-hydroxo)bis(mu-pyrazolato) complex, Tp(Pri2)V(O)(mu-OH)(mu-Pz(Pri2))V(O)(mu-OH)(mu-Pz(Pri2))V(O)Tp(Pri2) (5), were isolated. The hydroxo-aqua complex 4 was dimerized through the intermolecular hydrogen-bonding interaction between the hydroxo and aqua ligands forming the H3O2- bridging ligand. The trinuclear complex 5 consisted of two octahedral Tp(Pri2)V(O) fragments and a distorted trigonal-bipyramidal non-Tp(Pri2)-supported VO2+ center, sitting on the pseudo C-2 symmetry axis, and was formed via coupling of 4 and the VO2+-pyrazolato species, resulting from partial decomposition of the chloro complexes during the hydrolysis. Steric repulsion of the bulky Pr-i groups in Tp(Pri2) might hinder the formation of a dinuclear bis(mu u-hydroxo) complex like the Tp(H2) and Tp(Me2) derivatives. The dinuclear bis(mu-hydroxo) complex with the Tp(Me2) ligand, (kappa(3)-Tp(Me2))V(O)(mu-OH)(2)V(O)(kappa(2)-Tp(Me2)) (7), consisted of syn-arranged V=O fragments, having the different coordination geometries of the vanadium centers (octahedron with kappa(3)-Tp(Me2) and trigonal bipyramid with kappa(2)-Tp(Me2)). Intramolecular hydrogen-bending interaction between one of the two hydroxo groups and the noncoordinated pyrazolyl nitrogen atom in kappa(2)-Tp(Me2) was observed.