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Theoretical approaches to estimating homolytic bond dissociation energies of organocopper and organosilver compounds


Rijs, NJ and Brookes, NJ and O'Hair, RAJ and Yates, BF, Theoretical approaches to estimating homolytic bond dissociation energies of organocopper and organosilver compounds, Journal of Physical Chemistry A, 116, (35) pp. 8910-8917. ISSN 1089-5639 (2012) [Refereed Article]

Copyright Statement

Copyright 2012 American Chemical Society

DOI: doi:10.1021/jp305718z


Although organocopper and organosilver compounds are known to decompose by homolytic pathways among others, surprisingly little is known about their bond dissociation energies (BDEs). In order to address this deficiency, the performance of the DFT functionals BLYP, B3LYP, BP86, TPSSTPSS, BHandHLYP, M06L, M06, M06-2X, B97D, and PBEPBE, along with the double hybrids, mPW2-PLYP, B2-PLYP, and the ab initio methods, MP2 and CCSD(T), have been benchmarked against the thermochemistry for the M-C homolytic BDEs (D0) of Cu-CH3 and Ag-CH3, derived from guided ion beam experiments and CBS limit calculations (D0(Cu-CH3) = 223 kJ·mol -1; D 0(Ag-CH 3) = 169 kJ̇mol -1). Of the tested methods, in terms of chemical accuracy, error margin, and computational expense, M06 and BLYP were found to perform best for homolytic dissociation of methylcopper and methylsilver, compared with the CBS limit gold standard. Thus the M06 functional was used to evaluate the M-C homolytic bond dissociation energies of Cu-R and Ag-R, R = Et, Pr, iPr, tBu, allyl, CH2Ph, and Ph. It was found that D0(Ag-R) was always lower (~50 kJ·mol-1) than that of D0(Cu-R). The trends in BDE when changing the R ligand reflected the H-R bond energy trends for the alkyl ligands, while for R = allyl, CH2Ph, and Ph, some differences in bond energy trends arose. These trends in homolytic bond dissociation energy help rationalize the previously reported (Rijs, N. J.; O'Hair, R. A. J. Organometallics2010, 29, 2282-2291) fragmentation pathways of the organometallate anions, [CH3MR]-.

Item Details

Item Type:Refereed Article
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:Brookes, NJ (Dr Nigel Brookes)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:81605
Year Published:2012
Web of Science® Times Cited:5
Deposited By:Chemistry
Deposited On:2012-12-18
Last Modified:2017-10-25

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