Fischer Malte, Roy Matthew M D, Hüller Sascha, Schmidtmann Marc, Beckhaus Rüdiger
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Institut für Chemie, Fakultät für Mathematik und Naturwissenschaften, Carl von Ossietzky Universität Oldenburg, Postfach 2503, D-26111 Oldenburg, Germany.
Dalton Trans. 2022 Jul 19;51(28):10690-10696. doi: 10.1039/d2dt00014h.
The N-heterocyclic olefin (NHO) ImMeCH (2) (ImMeCH = (MeCNMe)CCH) was employed for the synthesis of the titanium complex 3 derived from an NHO ligand precursor. By reacting 2 with the bis(π-η:σ-η-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 (ImMeCH). 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.
N-杂环烯烃（NHO）ImMe₂CH（ImMe₂CH =（MeCNMe）C₂CH）用于合成源自NHO配体前体的钛配合物3。通过使2与双（π-η:σ-η-戊搭烯）钛配合物1a反应，2的末端叶立德型亚甲基单元被1a的一个戊搭烯配体的季外环碳原子去质子化，生成带有阴离子NHO配体（ImMe₂CH）的钛配合物3。通过核磁共振光谱、单晶X射线衍射和量子化学计算对3进行了表征。后者强调，3最好被描述为具有显著钛亚烷基共振结构贡献的钛乙烯基配合物。
