Nitrogen–Carbon Bond Formation by Reactions of a Titanium–Potassium Dinitrogen Complex with Carbon Dioxide, tert‐Butyl Isocyanate, and Phenylallene

Abstract

AbstractNitrogen–carbon bond‐forming reactions at coordinated dinitrogen in a bifunctional titanium–potassium system are reported. A titanium atrane complex with a tris(aryloxide)methyl ligand (1) was treated with two equivalents of potassium naphthalenide under N2 atmosphere to generate a bifunctional complex (2) in which N2 binds end‐on to two titanium centers and side‐on to three potassium cations. Dinitrogen complex 2 reacted with carbon dioxide, tert‐butyl isocyanate, and phenylallene, forming nitrogen–carbon bonds and affording diverse N‐functionalized products. The reaction of 2 with CO2 followed by addition of Me3SiCl resulted in the formation of the starting complex 1 with concomitant release of silylated carboxyl hydrazines while the reaction with two equivalents of tert‐butyl isocyanate proceeded by insertion into the Ti−N bonds. Treatment of 2 with phenylallene afforded vinyl‐substituted hydrazido complexes.