Syntheses and Characterization of Ti(III)/Ti(IV) Triazenido Complexes

Abstract

AbstractThe syntheses of side‐on Ti(III) triazenido complexes via the ethylene complexes Cp*Ti(η2‐C2H4)(η5‐C5H4CR2H) and side‐on Ti(IV) triazenido complexes via bis(π‐η5 : σ‐η1‐pentafulvene) titanium complexes are reported. The deprotonation of the triazene N−H function occurs under mild conditions either by reduction of the proton to hydrogen mediated via the masked titanocene (II) of the ethylene complex or by the nucleophilic Cexo atom of the pentafulvene moiety. The structures of the paramagnetic Ti(III) complexes were confirmed by single‐crystal X‐ray diffraction, whereas the diamagnetic Ti(IV) complexes were characterized via NMR spectroscopy and additionally, Ti2 c by single‐crystal X‐ray diffraction. The structure of complex Ti2 c reveals one of the smallest bent angles known for titanium pentafulvene complexes.