期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 882, 期 -, 页码 42-49出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2018.11.028
关键词
Decarboxylation; Desulfination; Organopalladium; Electrospray ionization; Mechanism; DFT calculation
资金
- Australian Research Council [DP180101187]
Routes to the formation of the 1,10-phenanthroline (phen) ligated organopalladium complexes [(phen) Pd(C6H5)](+) and [(phen)(2)Pd(C6H5)](+) via thermal extrusion of CO2 or SO2 from mono-nuclear, monocarboxylate or sulfinate complexes [(phen)(n)Pd(O2XC6H5)](+) (X = C or S; n = 1 and 2) are examined using a combination of low energy collision induced dissociation experiments in an ion trap mass spectrometer and DFT calculations. [(phen)Pd(C6H5)](+) is formed from both [(phen)Pd(O2CC6H5)](+) and [(phen)Pd(O2SC6H5)](+), but only [(phen)(2)Pd(O2SC6H5)](+) fragments to form [(phen)(2)Pd(C6H5)](+). In contrast, [(phen)(2)Pd(O2CC6H5)](+) fragments via loss of a phen ligand to form [(phen)Pd(O2CC6H5)](+). The experimental results are consistent with DFT calculations, which show that the barriers associated with the desulfination reactions are lower than those for the decarboxylation reactions. Of the organopalladium cations [(phen)Pd(C6H5)](+) and [(phen)(2)Pd(C6H5)](+), only the three-coordinate complex reacts with pyridine via a ligand coordination reaction to yield [(phen)Pd(C6H5) (NC5H5)](+) and with formic acid via an acid-base reaction to form [(phen)Pd(O2CH)](+). DFT calculations highlight that the former reaction energy is -48 kcal/mol while the later reaction proceeds via a favourable six-centered transition structure. (C) 2018 Elsevier B.V. All rights reserved.
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