Structural diversity of chlorido methoxido- and ethoxido-oxidovanadium(V) complexes: Two-dimensional network, dimer, and unusual syn-oriented V=O functionality

The syntheses and structural characterization of methoxido- and ethoxido-vanadium complexes [VOCl2(OMe)(HOMe)2] (1), [VOCl(OMe)2]2 (2), and [{VOCl(OEt)2}2(THF)] (3) are described. The effects of the reactant ratio, starting materials, and reaction media on the formation of the alkoxido oxidovanadium and their molecular structures are reported. Complex 1 was prepared by reaction of VOCl3 with three equiv of MeOH in pentane. In the solid state, each molecule of 1 is linked with four symmetry related molecules through four O–H···Cl interactions resulting in the formation of a 2D infinite network. Reaction of VOCl3 with 2 equiv of NaOMe in pentane yields the dimeric complex 2, which features a pair of methoxido bridges in the molecular structure. In THF, reaction of VOCl3 with 2 equiv of NaOEt results in a very thermolabile [{VOCl(OEt)2}2(THF)] (3), which adopts a butterfly conformation in the molecular structure and features an interesting alkoxido oxidovandium with syn-orientated V=O functionality.