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. Stepwise nitrogen-carbon bond formation at coordinated N proceeded to afford an unsymmetric hydrazido complex upon sequentially treating the dinitrogen complex with CS and CO . Addition of Me SiCl to the dicarboxylated hydrazido complex resulted in partial silylation of the carboxylate groups but did not lead to removal of the functionalized N 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.