Hydrolysis of nerve agents by model nucleophiles: a computational study.
Density functional theory calculations were employed to study the reaction of five nerve agents with model nucleophiles, including EtX(-) and EtXH (X=O, S, Se) for serine, cysteine and selenocysteine, respectively. Calculations at the B3LYP/6-311++G(2d,p) level of theory predict an exothermic reaction between ethoxide and all of the nerve agents studied. As compared to EtO(-) as a nucleophile, these reactions become approximately 30 kcal/mol more endothermic for EtS(-), and by approximately 40 kcal/mol for EtSe(-). The equivalent reactions with the neutral nucleophiles (EtXH) were more endothermic. The effect of solvation on the reaction thermochemistry was determined using a polarizable continuum model simulating the dielectric constant of chloroform. While there was a large exothermic shift for reactions involving charged nucleophiles with solvation modeling, the corresponding shift was minimal for the reaction with neutral nucleophiles.
Department of Chemistry, The Ohio State University, 100 W. 18th Avenue, Columbus, OH 43210, USA.
Jeremy M
JM
Beck
Christopher M
CM
Hadad
D002619:Chemical Warfare Agents / Q000737:chemistry*; D006868:Hydrolysis; D009946:Organothiophosphorus Compounds / Q000737:chemistry; D012524:Sarin / Q000737:chemistry; D012999:Soman / Q000737:chemistry
D002619:Chemical Warfare Agents; D009946:Organothiophosphorus Compounds; D012524:Sarin; D012999:Soman; C009680:VX-agent