Structural Characterization and Self-Association of (Arylimido)vanadium(V) Triisopropoxides

(Arylimido)vanadium(V) triisopropoxides, [( p-RC 6H 4N)V(O (i) Pr) 3] (R = NMe 2, OMe, H, CN, NO 2, Br), were prepared by the reaction of VO(O (i) Pr) 3 with the aryl isocyanates without solvent. The structures of the (arylimido)vanadium(V) triisopropoxides were characterized by single-crystal X-ray structure determination to elucidate the substituent effect on the self-association properties. Controlled association of the (arylimido)vanadium(V) triisopropoxides to the mu-oxo-bridged dimer complexes or the mu-imido-bridged dinuclear complex was achieved by changing the p-substituent on the benzene rings, which regulates the nature of the imido bonds. Furthermore, the one-dimensional linear polymer complex or the one-dimensional zigzag one through mu-oxo-bridging was formed in a solid state with the bimetallic (arylimido)vanadium(V) complex, [( (i) PrO) 3V(N- p-C 6H 4N)V(O (i) Pr) 3] or [( (i) PrO) 3V(N- m-C 6H 4N)V(O (i) Pr) 3], respectively.