Journal
RAPID COMMUNICATIONS IN MASS SPECTROMETRY
Volume 25, Issue 14, Pages 2083-2088Publisher
WILEY-BLACKWELL
DOI: 10.1002/rcm.5087
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Funding
- ARC [DP110103844, DP1096134]
- Faculty of Science
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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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