Lin Che-Hung, Pursley Dominik, Klein Johannes E M N, Teske Johannes, Allen Jennifer A, Rami Fabian, Köhn Andreas, Plietker Bernd
Institut für Organische Chemie , Universität Stuttgart , Pfaffenwaldring 55 , DE-70569 Stuttgart , Germany . Email:
Mettler-Toledo GmbH , Ockerweg 3, D-35396 Giessen , Germany.
Chem Sci. 2015 Dec 1;6(12):7034-7043. doi: 10.1039/c5sc02342d. Epub 2015 Sep 3.
The base metal complex BuN[Fe(CO)(NO)] (TBA[Fe]) catalyzes the rearrangement of vinyl and arylcyclopropanes both under thermal or photochemical conditions to give the corresponding vinyl or aryldihydrofurans in good to excellent yields. Under photochemical conditions the reaction is performed at room temperature. Spectroscopic investigations show that the metal carbonyl catalyst is not decarbonylated. The best performance was observed at a wavelength of 415 nm. icMRCI+Q analysis of the excited singlet and triplet states of the [Fe(CO)(NO)] anion was performed and used to calculate the vertical excitation energies which are in good agreement with the experimental data. CASSCF analysis indicates that the Fe center in all excited states of the ferrate becomes more electrophilic while adopting a distorted tetrahedral configuration. Both aspects have a positive synergistic effect on the formation of the initial π-complex with the incoming organic substrate.
贱金属配合物BuN[Fe(CO)(NO)]（TBA[Fe]）在热或光化学条件下均能催化乙烯基和芳基环丙烷的重排反应，以良好至优异的产率生成相应的乙烯基或芳基二氢呋喃。在光化学条件下，反应在室温下进行。光谱研究表明，金属羰基催化剂未发生脱羰反应。在波长为415 nm时观察到最佳性能。对[Fe(CO)(NO)]阴离子的激发单重态和三重态进行了icMRCI+Q分析，并用于计算垂直激发能，计算结果与实验数据吻合良好。CASSCF分析表明，高铁酸盐所有激发态中的铁中心在采用扭曲的四面体构型时变得更具亲电性。这两个方面对与进入的有机底物形成初始π配合物具有积极的协同作用。
