Hydrolytic and Peroxyhydrolytic Degradation of Nerve Agent Analogs with Low Molecular Weight Bimetallic Catalysts

摘要

The proposed research focused on the detoxification of both G- and V- types nerve agents by chemical means. Two key objectives are (i) developing novel hetero-bimetallic Fe/Zn TACN complexes that facilitate efficient hydrolysis of both organophosphate esters and G-agents, and (ii) synthesizing Mn2-complexes of TACN and probe their activities in catalyzing oxidative degradation of VX-simulants (sulfides) using eitherO2 or H2O2. Early on, we succeeded in the preparation of the tethered bis-TACN ligands. However, clean synthesis of hetero-bimetallic Fe/Zn complexes remains a challenge. The effort during the later stage (2002-2004) was focused on the activation of H2O2 and tBuO2H for the oxygenation of organic sulfides, which is the key step in V- agent degradation. Proficiency of bimetallic Mn-TACN system was explored and the effect of co-catalysts was evaluated. It is also found that the mononuclear Mn-TACN system can activate tBuO2H and exhibits one of the highest TOFs (turn- over frequency) in the oxygenation of sulfides by tBuO2H. Also identified is an organic soluble polyoxometallate catalyst,(Bu4N) 4GAMMA-SiW10O34(H2O)2, which displays both a remarkable 100% utility of H2O2 in catalytic sulfide oxygenation and chemical selectivity for sulfoxide formation. Several graduate and undergraduate students (both female and underrepresented groups) participated all phases of ARO funded research.