Reaction of Ti(N<sub>2</sub><sup>iPr</sup>N)(NNPh<sub>2</sub>)(py) with Ph(R)SiH<sub>2</sub> (R = H, Ph) or 9-BBN gave reductive
cleavage of the N<sub>α</sub>–N<sub>β</sub> bond
and formation of new silyl- or boryl-amido ligands. The corresponding
reactions of Cp*Ti{MeC(N<sup>i</sup>Pr)<sub>2</sub>}(NNR<sub>2</sub>) (R = Me or Ph) with HBPin or 9-BBN gave borylhydrazido-hydride
or borylimido products, respectively. N<sub>α</sub> and N<sub>β</sub> atom transfer and dehydrogenative coupling reactions
are also reported