Department of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P.R. China.
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, GA, 30322, USA.
Angew Chem Int Ed Engl. 2017 Apr 10;56(16):4473-4477. doi: 10.1002/anie.201700159. Epub 2017 Mar 21.
A novel double-anion complex, H [(CH ) N] [PNb O (V O) ⋅(V O ) ]⋅22 H O (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 H O with a turnover frequency (TOF) of 16 000 h . 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.
一种新型的双核阴离子配合物，H [(CH ) N] [PNb O (V O) ⋅(V O ) ]⋅22 H O（1），基于双帽聚氧铌酸盐和四核聚氧钒酸盐，通过常规技术合成，用于化学战剂的催化净化。在温和条件下，1 可以催化神经毒剂模拟物二乙基氰膦酸酯（DECP）的水解和芥子气模拟物 2-氯乙基乙基硫醚（CEES）的选择性氧化。在氧化净化体系中，使用近化学计量的 3%水合 H O 选择性地将 100% CEES 转化为无毒的 2-氯乙基乙基亚砜和乙烯基乙基亚砜，其转化频率（TOF）为 16000 h 。重要的是，即使经过十次循环，催化活性仍然保持，并且在 3 分钟内 CEES 完全被净化，没有形成剧毒的砜副产物。提出了一个三步氧化机制。
