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 N2 with CO2 and CS2 through formation of N-C bonds. Treatment of a naphthalene complex with N2 gave an end-on bridging dinitrogen complex featuring a [Ti2 K2 N2 ] core. The dinitrogen complex underwent insertion of CO2 into each Ti-NN bond to afford an N,N'-dicarboxylated hydrazido complex. Stepwise nitrogen-carbon bond formation at coordinated N2 proceeded to afford an unsymmetric hydrazido complex upon sequentially treating the dinitrogen complex with CS2 and CO2 . Addition of Me3 SiCl to the dicarboxylated hydrazido complex resulted in partial silylation of the carboxylate groups but did not lead to removal of the functionalized N2 unit from the metal centers. However, reduction of the dicarboxylated hydrazido complex with potassium naphthalenide afforded an oxo-bridged dinuclear complex along with release of free potassium cyanate.

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.