Deng Guohai, Pan Sudip, Wang Guanjun, Zhao Lili, Zhou Mingfei, Frenking Gernot
Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200438, China.
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, 211816, China.
Angew Chem Int Ed Engl. 2020 Oct 5;59(41):18201-18207. doi: 10.1002/anie.202007241. Epub 2020 Aug 13.
The reactions of laser-ablated beryllium atoms with dinitrogen and carbon monoxide mixtures form the end-on bonded NNBeCO and side-on bonded (η -N )BeCO isomers in solid argon, which are predicted by quantum chemical calculations to be almost isoenergetic. The end-on bonded complex has a triplet ground state while the side-on bonded isomer has a singlet electronic ground state. The complexes rearrange to the energetically lowest lying NBeNCO isomer upon visible light excitation, which is characterized to be an isocyanate complex of a nitrene derivative with a triplet electronic ground state. A bonding analysis using a charge- and energy decomposition procedure reveals that the electronic reference state of Be in the NNBeCO isomers has an 2s 2p excited configuration and that the metal-ligand bonds can be described in terms of N →Be←CO σ donation and concomitant N ←Be→CO π backdonation. The results demonstrate that the activation of N with the N-N bond being completely cleaved can be achieved via coupling with carbon monoxide mediated by a main group atom.
在固态氩中，激光烧蚀的铍原子与氮气和一氧化碳混合物的反应形成了端基键合的NNBeCO和侧基键合的(η -N )BeCO异构体，量子化学计算预测它们几乎具有相同的能量。端基键合的配合物具有三重态基态，而侧基键合的异构体具有单重态电子基态。在可见光激发下，这些配合物重排为能量最低的NBeNCO异构体，其特征是具有三重态电子基态的氮烯衍生物的异氰酸酯配合物。使用电荷和能量分解程序进行的键合分析表明，NNBeCO异构体中Be的电子参考态具有2s 2p激发构型，并且金属-配体键可以用N →Be←CO σ给予和伴随的N ←Be→CO π反馈来描述。结果表明，通过主族原子介导的与一氧化碳的偶联，可以实现N-N键完全断裂的N的活化。
