Publication: Bond Dissociation Energies of Solvated Silver(I)−Amide Complexes: Competitive Threshold Collision-Induced Dissociations and Calculations

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Title	Bond Dissociation Energies of Solvated Silver(I)−Amide Complexes: Competitive Threshold Collision-Induced Dissociations and Calculations
Authors/Editors*	Vladimir Romanov, Chi-Kit Siu, Udo H. Verkerk, Alan C. Hopkinson, K. W. Michael Siu
Where published*	J. Phys. Chem. A,
How published*	Journal
Year*	2010
Volume	114
Number	26
Pages	6964-6971
Publisher
Keywords
Link	http://pubs.acs.org/doi/full/10.1021/jp102470x
Abstract	Using competitive threshold collision-induced dissociation (TCID) measurements, experimental bond dissociation energies have been evaluated for the water, methanol, and acetonitrile adducts of silver(I)−amide complexes. The influence of the solvent molecules on the binding energy of silver(I) to acetamide, N-methylacetamide, and N,N-dimethylacetamide was investigated. Experimental results show that solvents decrease the amide binding energy by 4−6 kcal mol−1. Using density functional theory (DFT), binding energies were evaluated using nine functionals, after full geometry optimizations with the ECP28MWB basis set for silver and the 6-311++G(2df,2pd) basis set for the other atomic constituents of the ligands. In addition, calculations employing the DZVP basis set for Ag and DZVP2 for C, H, N, and O atoms at the B3LYP and MP2 levels of theory were used to investigate the influence of the basis set on the theoretical bond energies. A comparison of the experimental and theoretical silver(I)−ligand bond dissociation energies enables an assessment of the limitations in the basis sets and functionals in describing the energetics of the metal−solvent interaction and the metal−amide interaction. No single functional/basis set combination was found capable of predicting binding energies with a sufficiently high level of accuracy for the silver(I)−amide solvent complexes.

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