A new phosphotungstate-supported rhenium carbonyl derivative: synthesis, characterization and catalytic selective oxidation of thiophenes

Abstract

A monomeric phosphotungstate-supported rhenium carbonyl derivative, [N(CH₃)₄]₆H₄[P₂W₁₇O₆₂{Re(CO)₃}₂]·25H₂O (1), has been synthesized in a conventional solution system and structurally characterized by single crystal X-ray diffraction crystallography, IR spectroscopy, thermogravimetric (TG) analyses, X-ray powder diffraction (XRPD), and electrospray ionization mass spectrometry (ESI-MS). To our knowledge, this is the first time that the {Re₂} fragment existing in the polyoxoanion has been observed in polyoxometalate-supported metal carbonyl derivatives. Moreover, UV-vis spectroscopy was employed to elucidate the stability of the polyoxoanion, and its electrochemical properties were also investigated. In particular, complex 1 could act as an efficient homogeneous catalyst for selective oxidation of thiophenes. For example, dibenzothiophene (DBT) undergoes up to 99% conversion and 99% sulfone selectivity in acetonitrile with 30% H₂O₂ as an oxidant.