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Desulfination versus decarboxylation as a means of generating three- and five-coordinate organopalladium complexes [(phen)nPd(C6H5)]+ (n = 1 and 2) to study their fundamental bimolecular reactivity

Citation

Wang, Z and Yang, Y and Donnelly, DA and Canty, AJ and O'Hair, RAJ, Desulfination versus decarboxylation as a means of generating three- and five-coordinate organopalladium complexes [(phen)nPd(C6H5)]+ (n = 1 and 2) to study their fundamental bimolecular reactivity, Journal of Organometallic Chemistry, 882 pp. 42-49. ISSN 0022-328X (2019) [Refereed Article]

Copyright Statement

Copyright 2018 Elsevier B.V.

DOI: doi:10.1016/j.jorganchem.2018.11.028

Abstract

Routes to the formation of the 1,10-phenanthroline (phen) ligated organopalladium complexes [(phen)Pd(C6H5)]+ and [(phen)2Pd(C6H5)]+ via thermal extrusion of CO2 or SO2 from mono-nuclear, mono-carboxylate or sulfinate complexes [(phen)nPd(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)2Pd(O2SC6H5)]+ fragments to form [(phen)2Pd(C6H5)]+. In contrast, [(phen)2Pd(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)2Pd(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.

Item Details

Item Type:Refereed Article
Keywords:decarboxylation, desulfination, palladium, organopalladium, electrospray ionization, mechanism, DFT calculation, mass spectrometry, density functional theory
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
ID Code:130062
Year Published:2019
Deposited By:Chemistry
Deposited On:2019-01-09
Last Modified:2019-12-09
Downloads:0

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