Hexaammineruthenium(II,III) and Pentaamminedinitrogenruthenium(II). A Hartree-Fock-Slater Study

Discrete variation method Hartree-Fock-Slater studies are reported for the title compounds. The significant covalency and strong π back-bonding in the dinitrogen complex are apparent from populations, energy shifts, optical spectra, and reorganization effects on optical excitation; the energy levels are strongly perturbed by the strong covalency from their pseudooctahedral crystal field values. Transition-state calculations yield optical and photoemission results in good agreement with experiments. In the dinitrogen compound, the directly bonded N is considerably more negative, in agreement with simple electrostatic and bonding arguments.