Exploring energetics of dirhodium paddlewheel complexes with π-ligands of different topologies

Publication date: 1 November 2017 Source:Journal of Organometallic Chemistry, Volumes 849–850 Author(s): Andrey Yu Rogachev, Jingbai Li, Marina A. Petrukhina The first comprehensive theoretical exploration of the energetics of the interaction between π-ligands with isolated multiple carbon-carbon bonds (acetylene and ethylene), aromatic (benzene), planar polyaromatic (naphthalene, acenaphthalene, pyrene), curved polyaromatic (corannulene) and closed-cage C60-fullerene systems and Lewis acidic [Rh2(O2CCF3)4] complex has been carried out. Importantly, two energy decomposition schemes (EDA-NOCV and NBO-NEDA) that are based on very different approaches and algorithms were utilized in order to shed light on the energy and nature of bonding. The total bonding energy was sequentially represented as a combination of attractive covalent (ΔEorb and ECT in EDA and NBO approaches, respectively) and ionic (ΔEelstat and EEL), as well as repulsive (ΔEPauli and ECO) terms. This approach provides a balanced and complete picture of bonding between two (or more) interacting molecular fragments. All computational methods applied unambiguously indicate that the actual stability of adducts formed by unsaturated hydrocarbons with the selected Lewis acidic dirhodium complex is indeed a multifaceted phenomenon. Important contributions come from a different interplay between attractive (ΔEorb vs. ΔEelstat or ECT vs. EEL) and repulsive (ΔEPauli or ECO) components of the bonding and from v...

Source: Journal of Organometallic Chemistry - October 10, 2017 Category: Chemistry Source Type: research