摘要
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 (R3Si–H) and stannanes (R3Sn–H). High precision thermochemical calculations (CBS-QB3) reveal the carbon–hydrogen bond dissociation energy of NADH (70.8 kcal·mol−1) to be lower than that of stannane (SnH4: 78.1 kcal·mol−1), approaching that of the elusive plumbane (PbH4: 68.9 kcal·mol−1). 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.
摘要译文
NADH模型和NADH在环境条件下减少卤代烃被报道为一种新型反应性，指向NADH / NADPH依赖性过程的迄今未知的破坏性途径。用无处不在的农药DDT，吸入麻醉剂氟烷和几种简单的卤化碳研究反应。卤化物 - 氢化物交换代表了通过传统合成试剂如硅烷（R 3 Si-H）和锡烷（R 3 Sn-H）还原卤代烃的生化等价物。高精度热化学计算（CBS-QB3）显示NADH的碳 - 氢键解离能（70.8kcal·mol -1 ）低于锡烷（SnH 4：78.1kcal·mol < sup> -1 ），接近难以捉摸的铅（PbH 4：68.9kcal·mol -1 ）。 NADH模型的合成可接近性，它们的低碳 - 氢键解离能以及它们在空气和水分存在下的脱卤活性推荐这些化合物作为目前用于合成的空气敏感或有毒金属氢化物的替代物。
Michael K.Denk;Nicholas S.MilutinovićMikhail Y.Dereviankin;. Reduction of halocarbons to hydrocarbons by NADH models and NADH[J]. Chemosphere, 2019,233: s 890-895