Nitroxyl as a ligand in ruthenium tetraammine systems: a density functional theory study

The properties of the free nitroxyl molecule and the nitroxyl ligand in Ru(II) tetraammines (trans[Ru(NH3)(4)(nitroxyl)(n)(L)](2+n) (n = nitroxyl charge; L = NH3, py, P(OEt)(3), H2O, Cl- and Br-)) were studied using density functional theory. According to the calculated conformational energies, HNO complexes are more stable than their deprotonated analogues, and the singlet configuration (trans-(1)[Ru(NH3)(4)(L)HNO](2+)) is lower in energy than the corresponding triplet (trans-(3)[Ru(NH3)(4)(L)HNO](2+)). An evaluation of the sigma and pi components of the L-Ru-HNO bond suggest that the increased stability of these orbitals and the enhanced contributions from the HNO orbitals correlate to shorter Ru-N(H)O distances and higher.Ru-HNO stretching frequencies. The stability of the Ru-HNO bond was also evaluated through a theoretical kinetic study of HNO dissociation from trans-(1)[Ru(NH3)(4)(L)HNO](2+). The order of the Ru-HNO bonding stability in trans-(1)[Ru(NH3)(4)(L)HNO](2+) as a function of L was found to be as follows: H2O > Cl- similar to Br- > NH3 > py > P(OEt)(3). This order parallels the order of the trans-effect and trans-influence series experimentally measured for L in octahedral complexes. The same trend was also observed using an explicit solvent model, considering the presence of both HNO and H2O molecules in the transition state. For this series, the calculated bond dissociation enthalpies for the Ru-HNO bonds are in the range 23.8 to 45.7 kcal mol(-1). A good agreement was observed between the calculated Delta G(double dagger) values for the displacement of HNO by H2O in trans-(1)[Ru(NH3)(4)(P(OEt)(3)HNO](2+) (23.4 kcal mol(-1)) and the available experimental data for the substitution reactions of trans[Ru(NH3)(4)(POEt)(3)(Lx)](2+) (19.4 to 24.0 kcal mol(-1) for Lx = isn and P(OET)(3), respectively).