Theoretical studies on O-insertion reactions of nitrous oxide with ruthenium hydride complexes

DFT calculations have been carried out to study the mechanism of the N2O O-insertion into the Ru-H bonds of ruthenium hydride complexes (dmpe)2Ru(H)(X) (X = OH, H). The reaction pathways for the formation of the monoinsertion product (dmpe)2Ru(H)(OH) and the bis(hydroxo) complex (dmpe)2Ru(OH)(OH), which were obtained directly from the reactions of N20 with the ruthenium hydride complexes, have been investigated in detail. Focus has been made to understand how the kinetically inert NO is activated by the hydride complexes. It is found that N20 is activated through the hydride ligand nucleophilically attacking the terminal nitrogen of N20 followed by coordination of the activated N20 via the O-end.