Hydrazido complexes prepared by methylation of an anionic end-on bridging dinitrogen dititanium complex.

Here we report stepwise methylation of end-on bridging dinitrogen to a hydrazido ligand to a pentamethylhydrazinium salt, which is mediated by a titanium system with a tripodal aryloxide supporting ligand. The results constitute a synthetic cycle for pentamethylhydrazinium formation from dinitrogen and methyl iodide. We also describe silylation of the dinitrogen complex and carboxylation of the hydrazido complex.