UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California, San Diego , La Jolla, California 92093-0358, United States.
Department of Applied Chemistry, Faculty of Chemistry, University of the Basque Country (UPV-EHU) , Donostia-San Sebastián, 20018 Gipuzkoa, Spain.
J Am Chem Soc. 2017 Jun 14;139(23):7753-7756. doi: 10.1021/jacs.7b04640. Epub 2017 Jun 1.
A straightforward strategy allows for the synthesis of storable bicyclic (alkyl)(amino)carbenes (BICAACs), which feature enhanced σ-donating and π-accepting properties compared to monocyclic (alkyl)(amino)carbenes (CAACs). Due to the bicyclo[2.2.2]octane skeleton, the steric environment around the carbene center is different from that of CAACs and similar to that observed in classical N-heterocyclic carbenes. The different electronic properties of BICAACs as compared to CAACs allow for ligand exchange reactions not only at a metal center, but also at main group elements.
一种直接的策略允许合成可储存的双环(烷基)(氨基)卡宾(BICAAC),与单环(烷基)(氨基)卡宾(CAAC)相比,它们具有增强的σ-供体和π-受体性质。由于双环[2.2.2]辛烷骨架,卡宾中心周围的空间环境与 CAAC 不同,与经典的 N-杂环卡宾相似。BICAAC 与 CAAC 相比的不同电子性质不仅允许在金属中心,而且还允许在主族元素上进行配体交换反应。