Binding energies of the silver ion to alcohols and amides: a theoretical and experimental study.
The silver ion binding energies to alcohols (methanol, ethanol, n-propanol, i-propanol, and n-butanol) and to amides (acetamide, N-methylacetamide, N, N-dimethylacetamide, formamide, N-methylformamide, and N, N-dimethylformamide) have been calculated using density functional theory (DFT) and measured using the threshold collision-induced dissociation (TCID) method. For DFT, the combined basis sets of ECP28MWB for silver and 6-311++G(2df,2pd) for the other atoms were found to be optimal using a series of test calculations on Ag (+) binding to methanol and to formamide. In addition, the Ag (+) binding energies of all ligands were evaluated with nine functionals after full geometric optimizations. TCID binding energies were measured using a triple quadrupole mass spectrometer. Reasonable to good agreements were obtained between the calculated and experimental silver(I) binding energies. Ligation of Ag (+) to the alcohols was primarily via the oxygen, although n-propanol and n-butanol exhibited additional, bidentate coordination via the CH hydrogens. By contrast, silver(I) binding to the amides was all monodentate via the carbonyl oxygen. There appears to be strong correlations between the binding energies and the polarizabilities of the ligands.
Romanov
Vladimir
V
Department of Chemistry and Centre for Research in Mass Spectrometry, York University, 4700 Keele Street, Toronto, Ontario, Canada.
Siu
Chi-Kit
CK
Verkerk
Udo H
UH
El Aribi
Houssain
H
Hopkinson
Alan C
AC
Siu
K W Michael
KW
D000438:Alcohols / Q000737:chemistry*; D000577:Amides / Q000737:chemistry*; D003198:Computer Simulation; D007477:Ions / Q000737:chemistry; D008024:Ligands; D008956:Models, Chemical; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*; D013816:Thermodynamics
D000438:Alcohols; D000577:Amides; D007477:Ions; D008024:Ligands; D012834:Silver