title: Bond dissociation energies of solvated silver(I)-amide complexes: competitive threshold collision-induced dissociations and calculations.
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.
authors.affiliation: Department of Chemistry and Centre for Research in Mass Spectrometry, York University, 4700 Keele Street, Toronto, Ontario, Canada M3J 1P3.
authors.forename: Vladimir
authors.initials: V
authors.lastname: Romanov
authors.forename: Chi-Kit
authors.initials: CK
authors.lastname: Siu
authors.forename: Udo H
authors.initials: UH
authors.lastname: Verkerk
authors.forename: Alan C
authors.initials: AC
authors.lastname: Hopkinson
authors.forename: K W Michael
authors.initials: KW
authors.lastname: Siu
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D000577:Amides / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D000097:Acetonitriles; D000577:Amides; D009942:Organometallic Compounds; D012997:Solvents; D014867:Water; D012834:Silver; D000432:Methanol; C032159:acetonitrile