PNNL

Abstract

The stoichiometric and catalytic reactions of Cu-H dimers supported by N-heterocyclic carbenes (NHCs) have mainly focused on the insertions of aldehydes, ketones, CO2, and unsaturated hydrocarbons. In this report, we investigated the stoichiometric reactions of dimeric [(NHC)CuH]2 (NHC = IPr*, 6Dipp) with unsaturated nitrogen-based substrates of PhN=NPh, N3Ad, pyrazine, and N2O. The spectroscopic and structural chacterizations of the resulting monomeric, two-coordinate Cu(I) complexes containing triazenido, diphenyl hydrazido, pyrazinyl, and hydroxide ligands are discussed. The hydrazido complex of (IPr*)Cu(NPh-NHPh) and triazenido complex of [(IPr*)Cu(HNNNAd)] are resistant to N-N bond cleavage and loss of N2, respectively, to form the corresponding amido complexes even when heated at 80 ºC over several hours.