Liu Heng, Khononov Maxim, Fridman Natalia, Tamm Matthias, Eisen Moris S
Schulich Faculty of Chemistry, Technion-Israel Institute of Technology . Haifa City 32000, Israel.
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig , Hagenring 30, 38106 Braunschweig, Germany.
Inorg Chem. 2017 Mar 20;56(6):3153-3157. doi: 10.1021/acs.inorgchem.7b00357. Epub 2017 Mar 8.
The insertion of alcohols into carbodiimides mediated by benzimidazolin-2-iminato actinide complexes [(BimN)AnN″] [N″ = N(SiMe)] is presented herein. Analysis of single-crystal data revealed that steric hindrance, rather than electronic properties, plays an important role in determining the accessibility for this insertion process. All actinide complexes showed excellent activities under very mild conditions. Stoichiometric reactions in combination with kinetic and thermodynamic studies allow us to propose a plausible active species and a mechanism for the catalytic cycle.
本文介绍了由苯并咪唑啉-2-亚氨基锕系配合物[(BimN)AnN″] [N″ = N(SiMe)]介导的醇插入碳二亚胺的反应。单晶数据分析表明，空间位阻而非电子性质在决定该插入过程的可及性方面起着重要作用。所有锕系配合物在非常温和的条件下均表现出优异的活性。化学计量反应与动力学和热力学研究相结合，使我们能够提出一个合理的活性物种和催化循环的机理。
