Vanadyl-Capped Polyoxoniobate Enabling Bifunctional Sustainable Synthesis of Disulfides and Phosphinothioates

The development of sustainable and multifunctional catalysts for atom-economic bond-forming reactions under mild conditions is highly desirable. Herein, we report a vanadyl-capped polyoxoniobate, denoted as HPOVNb, with the formula (H2en)4.155{[VNb12O40(VO)2][VNb12O40(VO)2.846][Cu(en)2]6}·7.5en·17H2O (en = ethylenediamine), that functions as a bifunctional and sustainable catalyst for both the oxidative coupling of thiophenols and the cross-dehydrogenative coupling between thiophenols and P(O)-H compounds. These reactions proceed efficiently at room temperature in green solvents without any external oxidant or energy input, achieving yields up to 96%. Notably, the catalyst enables the selective synthesis of unsymmetrical disulfides in up to 81% yield. This work demonstrates a versatile and sustainable catalytic system for S–S and P–S bond formation, expanding the application of polyoxoniobates in organosulfur synthesis.