期刊
RAPID COMMUNICATIONS IN MASS SPECTROMETRY
卷 25, 期 14, 页码 2083-2088出版社
WILEY-BLACKWELL
DOI: 10.1002/rcm.5087
关键词
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资金
- ARC [DP110103844, DP1096134]
- Faculty of Science
Previous studies have shown that highly reactive product ions formed by collision-induced dissociation (CID) of precursor ions generated via electrospray can readily react with residual solvent or drying gases, especially in ion trap mass spectrometers. Here we report on the rapid addition of nitrogen to the coordinatively unsaturated organoplatinum cation, [(phen)Pt(CH(3))](+) (phen = 1,10-phenanthroline) formed via decarboxylation of the acetate complex [(phen)Pt(O(2)CCH(3))](+). This contrasts with the related coordinatively unsaturated group 10 cations: addition of nitrogen to [(phen)Pd(CH(3))](+) occurs at longer reaction times, whereas addition of nitrogen to [(phen)Ni(CH(3))](+) is virtually non-existent. To better understand these reactions, density functional theory (DFT) calculations were carried out at the B3LYP/SDD6-31+G(d) level of theory to determine the N(2)-binding energies of [(phen)M(CH(3))](+). [(phen)Pt(CH(3))](+) has a higher binding energy to N(2) (1.06 eV) than either [(phen)Ni(CH(3))](+) (0.61 eV) or [(phen)Pd(CH(3))](+) (0.66 eV), consistent with the experimental ease of addition of nitrogen to the coordinatively unsaturated organometallic complexes, [(phen)M(CH(3))](+). Finally, [(phen)M(CH(3))](+) are reactive to other background gases, forming [(phen)M(O(2))](center dot+) (for M = Ni) in reactions with oxygen and undergoing water addition (for M = Ni, Pd and Pt) and water addition/CH(4) elimination reactions to yield [(phen)M(OH)](+) (for M = Ni and Pt). Copyright (C) 2011 John Wiley & Sons, Ltd.
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