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 [Ti2K2N2] 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 Me3SiCl 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. Carbon dioxide and carbon disulfide reacted with an end‐on bridging dinitrogen titanium/potassium complex though insertion into the Ti−NN bonds to form new nitrogen‐carbon bonds. Carboxylation with CO2 afforded a symmetric dicarboxylated hydrazido complex. On the other hand, stepwise C−N bond formation proceeded at coordinated N2 to generated an unsymmetric hydrazido complex upon sequentially treating with CS2 and then CO2.