期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 115, 期 48, 页码 14006-14012出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp2086736
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资金
- Natural Sciences and Engineering Research Council of Canada
- American Chemical Society
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 Delta H-acid degrees 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.
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