Nitrous oxide and dinitrogen complexes as intermediates in the decomposition of metal carbonyl nitrosyls: The triruthenium system

Abstract

The stability of some metal carbonyl nitrosyls is limited by the oxidation of CO groups by adjacent NO groups to eliminate CO2. Theoretical studies show how intermediates in such processes can be trapped as molecular species using the central Ru3 unit found in the stable and experimentally known Ru3(CO)10(µ-NO)2. Two stages of such NO reduction by adjacent CO ligands have been identified in the Ru3 system. The first stage, as demonstrated by conversion of Ru3(CO)10(µ-NO)2 to the N2O complex Ru3(CO)9(µ3-N2O), involves attack of the oxygen atom of an NO group on the carbon atom of an adjacent CO group to eliminate CO2. This leaves a reactive nitride ligand that can couple with a second NO group to form an N2O complex. The oxygen atom on such an N2O ligand can convert an adjacent CO group to CO2 thereby leaving behind a metal dinitrogen complex.