Exploring cation- π interaction in half sandwiches and sandwiches with XX triple bonds (XC, Si and Ge): A DFT study

Publication date: 1 September 2017 Source:Computational and Theoretical Chemistry, Volume 1115 Author(s): Nabajit Sarmah, Bhabesh Chandra Deka, Pradip Kr. Bhattacharyya Density functional theory (DFT) and MP2 calculation have been carried out in order to understand the ability of cation-π interaction to form half sandwiches and sandwiches of CC, SiSi and GeGe triple bond bridged via metal ions (Li+, Na+, K+, Mg2+ and Ca2+). Stability of such complexes is evaluated in terms of interaction energy and thermo-chemical parameters, enthalpy and free energy. Results predict a comprehensive stability of such half sandwiches/sandwiches in gas phase. In contrast to marked instability of complexes of other chosen cations in polar solvents, Mg2+ complexes are considerably stable. Thermo-chemical analysis suggests that in both the cases the complexation process is enthalpy as well as free energy driven. Impact of cation-π interaction on the chosen π-systems is assessed by computing IR and UV–Visible spectra (using time dependent density functional theory (TD-DFT)) of the π-systems and their respective complexes. Graphical abstract

Source: Computational and Theoretical Chemistry - July 29, 2017 Category: Chemistry Source Type: research