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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reactions of atomic metal anions in the gas phase: Competition between electron transfer, proton abstraction and bond activation
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Reactions of atomic metal anions in the gas phase: Competition between electron transfer, proton abstraction and bond activation

机译：气相中原子金属阴离子的反应：电子转移，质子抽象和键活化之间的竞争

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摘要

Bare metal anions K-, Rb-, Cs-, Fe -, Co-, Ni-, Cu-, and Ag -, generated by electrospray ionization of the corresponding oxalate or tricarballylate solutions, were allowed to react with methyl and ethyl chloride, methyl bromide, nitromethane, and acetonitrile in the collision hexapole of a triple-quadrupole mass spectrometer. Observed reactions include (a) the formation of halide, nitride, and cyanide anions, which was shown to be likely due to the insertion of the metal into the C-X, C-N, and C-C bonds, (b) transfer of H+ from the organic molecule, which is demonstrated to most likely be due to the simple transfer of a proton to form neutral metal hydride, and (c) in the case of nitromethane, direct electron transfer to form the nitromethane radical anion. Interestingly, Co- was the only metal anion to transfer an electron to acetonitrile. Differences in the reactions are related to the differences in electron affinity of the metals and the Δ_(acid)H° of the metals and organic substrates. Density functional theory calculations at the B3-LYP/6-311++G(3df,2p)//B3-LYP/6-31+G(d) level of theory shed light on the relative energetics of these processes and the mechanisms by which they take place.
机译：通过相应的草酸盐或三羧酸酯溶液的电喷雾电离产生的裸金属阴离子K-，Rb-，Cs-，Fe-，Co-，Ni-，Cu-和Ag-与甲基和乙基氯反应，三重四极杆质谱仪的碰撞六极杆中的甲基溴，硝基甲烷和乙腈。观察到的反应包括（a）卤化物，氮化物和氰化物阴离子的形成，这可能是由于金属插入CX，CN和CC键中引起的;（b）H +从有机分子中的转移，这很可能是由于质子的简单转移形成中性金属氢化物所致;（c）在硝基甲烷的情况下，直接电子转移形成了硝基甲烷自由基阴离子。有趣的是，Co-是将电子转移到乙腈中的唯一金属阴离子。反应的差异与金属的电子亲和力的差异以及金属和有机底物的Δ_（acid）H°有关。在B3-LYP / 6-311 ++ G（3df，2p）// B3-LYP / 6-31 + G（d）层次上的密度泛函理论计算揭示了这些过程的相对能量学及其机理通过它们发生。

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