A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

A novel double‐anion complex, H₁₃(CH₃)₄N]₁₂PNb₁₂O₄₀(V^VO)₂⋅(V^IV₄O₁₂)₂]⋅22 H₂O ( 1 ), based on bicapped polyoxoniobate and tetranuclear polyoxovanadate was synthesized, characterized by routine techniques and used in the catalytic decontamination of chemical warfare agents. Under mild conditions, 1 catalyzes both hydrolysis of the nerve agent simulant, diethyl cyanophosphonate (DECP) and selective oxidation of the sulfur mustard simulant, 2‐chloroethyl ethyl sulfide (CEES). In the oxidative decontamination system 100 % CEES was transformed selectively to nontoxic 2‐chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H₂O₂ with a turnover frequency (TOF) of 16 000 h⁻¹. Importantly, the catalytic activity is maintained even after ten recycles and CEES is completely decontaminated in 3 mins without formation of the highly toxic sulfone by‐product. A three‐step oxidative mechanism is proposed.