Quantum chemical study of the bond orders in the ruthenium, diruthenium and dirhodium nitrosyl complexes

Abstract: Density functional calculations with the B3LYP functional were carried out for the [Ru(NO)Cl5]2−, [Ru(NO)(NH3)5]3+, [Ru(NO)(CN)5]2−, [Ru(NO)(CN)5]3−, [Ru(NO)(hedta)] q (hedta= N-(hydroxyethyl)ethylenediaminetriacetate triple-charged anion; q =0,−1,−2), Rh2(O2CR)4, Rh2(O2CR)4(NO)2, Ru2(O2CR)4, Ru2(O2CR)4(NO)2, Ru2(dpf)4, and Ru2(dpf)4(NO)2 (dpf= N,N′-diphenylformamidinate ion; R=H, CH3, CF3) complexes. The electronic structure was analyzed in terms of Mayer and Wiberg bond order indices. The technique of bond order indices decomposition into σ-, π-, and δ-contributions was proposed. [Copyright &y& Elsevier]