A quantum chemical study of the structure of fluorinated silver acetate(I) monomers and dimers

• Published in: Journal of structural chemistry 2010-06, Vol.51 (3), p.409-418
• Main Authors: Bazhanova, Z. G., Tarasov, Yu. I., Kovtun, D. M., Boltalin, A. I., Novosadov, B. K., Kochikov, I. V.
• Format: Article
• Language: English
• Subjects: Atomic; Atomic/Molecular Structure and Spectra; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Molecular; Optical and Plasma Physics; Physical Chemistry; Solid State Physics
• ISSN: 0022-4766; 1573-8779
• DOI: 10.1007/s10947-010-0062-7

Quantum chemical calculations of the equilibrium structure, potential energy surface cross-sections along the nonrigid degrees of freedom of (CF 3 COOAg) 2 , (CHF 2 COOAg) 2 , (CH 2 FCOOAg) 2 , and (CH 3 COOAg) 2 dimers and the corresponding monomers are presented. The B3LYP method with the augmented cc-pVTZ basis set for C, O, F atoms and the Stuttgart 1997 RSC basis set together with the relativistic effective potential for Ag atoms is used. It is shown that in all dimers the eight-membered ring is a rather rigid planar fragment, and the Ag atoms can be bonded with the bond order of 0.2 in dimers. Almost free rotation of acyclic groups around the C-C bond in (CH 3 COOAg) 2 and (CF 3 COOAg) 2 dimers transforms into a hindered one in the (CHF 2 COOAg) 2 dimer, and further into the existence of syn - and anti -structures divided by a high rotation barrier in the (CH 2 FCOOAg) 2 dimer. In monomers, the ratio of the internal rotation barriers is similar. With increasing number of fluorine substitution for hydrogen atoms in dimers the Ag-Ag bond length is found to increase (2.79 Å, 2.81 Å, 2.83 Å, 2.84 Å) and the ring rigidity to simultaneously decrease in the acetate-triflouroacetate series.