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. Issue 28 (15th February 2022)

• Record Type: Journal Article
• Authors: Fischer, Malte; Roy, Matthew M. D.; Hüller, Sascha; Schmidtmann, Marc; Beckhaus, Rüdiger
• Is Part Of: Dalton transactions. Volume 51:Issue 28(2022)
• Page Start: 10690
• Page End: 10696
• Publication Date: 2022-02-15
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt00014h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Elucidating the bonding situation in a titanium complex with an anionic N-heterocyclic olefin ligand. Abstract : The N-heterocyclic olefin (NHO) ImMe4 CH2 (2 ) (ImMe4 CH2 = (MeCNMe)2 CCH2 ) was employed for the synthesis of the titanium complex 3 derived from an NHO ligand precursor. By reacting 2 with the bis(π–η 5 :σ–η 1 -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 (ImMe4 CH − ). 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.