The structure of dichlorotris(triphenylphosphine)ruthenium(II): a DFT study of interaction energies and substitution mechanism

The structure and substitution energies of dichlorotris(triphenylphosphine)ruthenium(II) complex, [RuCl2(PPh3)3], was computed with ten different methods at the density functional theory level using a composition basis sets. PBE0 led to best description bond lengths, while MN12-L yielded results for angles. For calculation Ru-P dissociation energies, were obtained M06-L functional. nature discussed in terms donation back-donation as well steric versus covalent contributions bonding. In square pyramidal structure, apical is considerably tighter than basal bonds. This due an interaction PPh3 ligand high d character orbital on Ru atom, favouring back-donation, leading short distance strong bonding energy. Additionally, we also investigated equilibrium structures mechanism one group by piperidine molecule. between several species involved process indicates that addition molecule [RuCl2(PPh3)3] followed elimination unity pathway lower