New ligand platforms for developing the chemistry of the Ti=N-NR2 functional group and the insertion of alkynes into the N-N bond of a Ti=N-NPh2 ligand.

Two broadly applicable strategies for extending the available ligand platforms of the virtually unexplored terminal Ti=N-NR2 functional group are described, along with the highly selective room temperature insertion of alkynes into the N-N bond of Ti{MeN(CH2CH2NSiMe3)2}(NNPh2)(py) and the catalytic cis-diamination of PhC[triple bond]CMe by diphenylhydrazine.