Theoretical Studies on O-Insertion Reactions of Nitrous Oxide with Ruthenium Hydride Complexes

Abstract

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 N2O with the ruthenium hydride complexes, have been investigated in detail. Focus has been made to understand how the kinetically inert N2O is activated by the hydride complexes. It is found that N2O is activated through the hydride ligand nucleophilically attacking the terminal nitrogen of N2O followed by coordination of the activated N2O via the O-end