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

Abstract Here we show that a tridentate bis(aryloxide)anilide‐ligated titanium/potassium scaffold promotes functionalization of coordinated N 2 with CO 2 and CS 2 through formation of N−C bonds. Treatment of a naphthalene complex with N 2 gave an end‐on bridging dinitrogen complex featuring a [Ti 2 K 2 N 2 ] core. The dinitrogen complex underwent insertion of CO 2 into each Ti−NN bond to afford an N , N ′‐dicarboxylated hydrazido complex. Stepwise nitrogen‐carbon bond formation at coordinated N 2 proceeded to afford an unsymmetric hydrazido complex upon sequentially treating the dinitrogen complex with CS 2 and CO 2 . Addition of Me 3 SiCl to the dicarboxylated hydrazido complex resulted in partial silylation of the carboxylate groups but did not lead to removal of the functionalized N 2 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.