Department of Chemistry, University of Guelph, 50 Stone Road E., Guelph, Ontario, N1G 2W1, Canada.
Department of Chemistry, University of Guelph, 50 Stone Road E., Guelph, Ontario, N1G 2W1, Canada.
Chemosphere. 2019 Oct;233:890-895. doi: 10.1016/j.chemosphere.2019.05.169. Epub 2019 May 28.
The reduction of halocarbons by NADH models and NADH under ambient conditions is reported as a new type of reactivity pointing towards a hitherto unknown disruptive pathway for NADH/NADPH-dependent processes. The reaction was studied with the omnipresent pesticide DDT, the inhalation anesthetic halothane, and several simple halocarbons. The halide-hydride exchange represents a biochemical equivalent for the reduction of halocarbons by traditional synthetic reagents like silanes (RSi-H) and stannanes (RSn-H). High precision thermochemical calculations (CBS-QB3) reveal the carbon-hydrogen bond dissociation energy of NADH (70.8 kcal·mol) to be lower than that of stannane (SnH: 78.1 kcal·mol), approaching that of the elusive plumbane (PbH: 68.9 kcal·mol). The ready synthetic accessibility of NADH models, their low carbon-hydrogen bond dissociation energy, and their dehalogenation activity in the presence of air and moisture recommend these compounds as substitutes for the air-sensitive or toxic metal hydrides currently employed in synthesis.
在环境条件下，通过 NADH 模型和 NADH 还原卤代烃的反应被报道为一种新的反应类型，指向了一种迄今为止未知的破坏 NADH/NADPH 依赖性过程的途径。该反应使用普遍存在的杀虫剂滴滴涕、吸入麻醉剂氟烷和几种简单的卤代烃进行了研究。卤化物-氢化物交换代表了通过传统合成试剂（如硅烷 (RSi-H) 和锡烷 (RSn-H)）还原卤代烃的生物化学等效物。高精度热化学计算 (CBS-QB3) 表明 NADH (70.8 kcal·mol) 的碳氢键离解能低于锡烷 (SnH：78.1 kcal·mol)，接近难以捉摸的铅烷 (PbH：68.9 kcal·mol)。NADH 模型的易于合成、较低的碳氢键离解能以及它们在空气和水分存在下的脱卤活性，使这些化合物成为目前用于合成的空气敏感或有毒金属氢化物的替代品。
