Cleavage of the CN Bond on a Triruthenium Cluster: Synthesis and Structure of a Triruthenium Complex Containing a μ3-Nitrido Ligand

摘要

Since a nitrile group contains an sp hybridized nitrogen atom as well as dinitrogen, cleavage of the CN bond of nitrile is regarded as an analogue of NN bond activation of dinitrogen. The nitrogenase enzyme was shown to catalyze reductive cleavage of the CN bond of nitrile.[1] Carbon-nitrogen bond cleavage of nitrile by using the dimolybdenum sulfido complex [(CpMo)2(S2CH2)(-S)(-SH)]+ (Cp=5-C5H5) under a dihydrogen atmosphere was demonstrated by Rakowski DuBois and co-workers.[2] Heterolytic cleavage of dihydrogen by the sulfido complex was proposed as a prerequisite for further CN bond cleavage. In general, the electronic property of the hydrido ligand continuously changes from protonic to hydridic depending upon whether it is combined with a metal center, thus the polyhydrido cluster effectively cleaves the CN bond of nitrile. We report herein cleavage of the CN bond of nitrile in the reaction of a triruthenium hydrido complex.