Reaction of a bis(pentafulvene)titanium complex with an N-heterocyclic olefin: C–H-activation leads to resonance between a titanium vinyl and titanium alkylidene complex

Abstract

The N-heterocyclic olefin (NHO) ImMe₄CH₂ (2) (ImMe₄CH₂ = (MeCNMe)₂CCH₂) was employed for the synthesis of the titanium complex 3 derived from an NHO ligand precursor. By reacting 2 with the bis(π–η⁵:σ–η¹-pentafulvene)titanium complex 1a, the terminal ylidic methylene unit of 2 is deprotonated by the quaternary exocyclic carbon atom of one pentafulvene ligand of 1a yielding the titanium complex 3 which bears an anionic NHO ligand (ImMe₄CH⁻). 3 was characterized by NMR spectroscopy, single crystal X-ray diffraction and quantum chemical calculations. The latter highlight that 3 is best described as a titanium vinyl complex with significant contribution of the titanium alkylidene resonance structure.