Dinitrogen Functionalization with Carbon Dioxide and Carbon Disulfide Giving Symmetric and Unsymmetric Hydrazido Complexes.

Here we show that a tridentate bis(aryloxide)anilide-ligated titanium/potassium scaffold promotes functionalization of coordinated N with CO and CS through formation of N-C bonds. Treatment of a naphthalene complex with N gave an end-on bridging dinitrogen complex featuring a [Ti K N ] core. The dinitrogen complex underwent insertion of CO into each Ti-NN bond to afford an N,N'-dicarboxylated hydrazido complex.

Systematic reductive oligomerization of isocyanides with a vanadium(ii) complex.

Using a V(ii) complex as a reducing reagent, we demonstrate controlled reduction of isocyanides, resulting in decyanation of alkyl isocyanides to form a V(iii) cyanide complex or oligomerization of aryl isocyanides to form trimers and a tetramer. The pathways leading to the trimers involve a divanadium ynediamido intermediate, which further reacts with the third isocyanide molecule to selectively produce a tri(imino)deltate or an indolenine complex, by altering the temperature and stoichiometry.