Synthesis and characterization of some oxovanadium(V) complexes with internally functionallized oximes. Crystal and molecular structure of heptacoordinated [VOCl{ON=C(CH₃) (C₄H₃S-2)}₂] · CH₃OH

Sharma, V., Bohra, R., Drake, J.E., Hursthouse, M.B., Light, M.E. and Bingham, A.L. (2007) Synthesis and characterization of some oxovanadium(V) complexes with internally functionallized oximes. Crystal and molecular structure of heptacoordinated [VOCl{ON=C(CH₃) (C₄H₃S-2)}₂] · CH₃OH. Transition Metal Chemistry, 32 (4), 442-448. (doi:10.1007/s11243-007-0182-x).

Abstract

New heteroleptic oxovanadium(V) chloro oximato complexes of the type [VOCl_3-n {ON=C(CH₃)(Ar)}_n] (where Ar = C₄H₃O-2, C₄H₃S-2, C₅H₄N-2 and n = 1 or 2) have been synthesized in excellent yields by the reaction of VOCl₃ with the sodium salts of corresponding internally functionallized oximes in refluxing anhydrous benzene. The complexes are characterized by elemental analyses and spectroscopic techniques (FT-IR, 1H-, ¹³C{¹H}- and ⁵¹V-NMR). FAB mass spectral analysis of one of the derivatives, [VOCl{ON=C(CH₃)C₄H₃S}₂] indicates the monomeric nature of the complex. 51V-NMR spectral studies of these complexes suggest tetra-coordination around the vanadium atom in solution. However, the single crystal X-ray diffraction study of a redistribution product [VOCl{ON=C(CH₃)(C₄H₃S-2)}₂] · CH₃OH obtained on recrystallization of [VOCl₂{ON=C(CH₃)(C₄H₃S-2)}] from a methanol-hexane mixture shows the vanadium(V) atom is hepta-coordinated with distorted pentagonal bipyramidal geometry. The oxo-atom occupies the axial position while the weakly coordinated CH₃OH group is trans to the V=O atom. The two oximato ligands in the approximate pentagonal plane are bonded to the central vanadium atom in dihapto (η₂-N, O) manner with the formation of three-membered rings. The V–Cl bond occupies the fifth position in the approximate plane.

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Contributors

Author: M.E. Light

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