Reactions of Atomic Metal Anions in the Gas phase: Competition between Electron Transfer, Proton Abstraction and Bond Activation

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• 作者：Sharon Curtis ; Jason DiMuzio ; Alex Mungham ; Julie Roy ; Dhiya Hassan ; Justin Renaud ; Paul M. Mayer
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：December 8, 2011
• 年：2011
• 卷：115
• 期：48
• 页码：14006-14012
• 全文大小：859K
• 年卷期：v.115,no.48(December 8, 2011)
• ISSN：1520-5215

文摘

Bare metal anions K^{鈥?/sup>, Rb鈥?/sup>, Cs鈥?/sup>, Fe鈥?/sup>, Co鈥?/sup>, Ni鈥?/sup>, Cu鈥?/sup>, and Ag鈥?/sup>, 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鈥揦, C鈥揘, and C鈥揅 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鈥?/sup> 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 螖b>acidb>H掳 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.}