Synthesis and spectroscopic characterization of a Keggin α-1,4,9-trivanadium-substituted polyoxotungstate-supported Cp*Rh2+ complex, [(Cp*Rh)(α-1,4,9-PW9V3O40)]4−

Abstract

A novel Keggin polyoxotungstate-based 1∶1-type Cp*Rh²⁺ complex (Cp* = C₅Me₅), [Cp*Rh(DMSO)₃]H₂[(Cp*Rh)(α-1,4,9-PW₉V₃O₄₀)]·3DMSO·0.5MeCN 2, was synthesized by reaction in MeCN–DMSO mixed solvent at 80 °C under nitrogen, of the α-Keggin-type 1,4,9-trivanadium-substituted polyoxotungstate (NBu₄)₄H₂[α-1,4,9-PW₉V₃O₄₀] 1 with [Cp*Rh(MeCN)₃]²⁺. Characterization was performed with complete elemental analysis, TG/DTA, FTIR, and multiple (⁵¹V, ³¹P, ¹H and ¹³C) NMR spectroscopies. Complex 2 contains two different types of Cp*Rh²⁺ groups; one is covalently bonded to the surface oxygen atoms of three edge-shared vanadium octahedra while the other is present as a DMSO-solvated counter ion. The composition of complex 2 is unique and can be compared with previous Keggin and Dawson polyoxotungstate-based organometallic complexes.