Wang Qian, Pan Sudip, Lei Shujun, Jin Jiaye, Deng Guohai, Wang Guanjun, Zhao Lili, Zhou Mingfei, Frenking Gernot
Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, 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.
Nat Commun. 2019 Jul 29;10(1):3375. doi: 10.1038/s41467-019-11323-5.
We report the isolation and spectroscopic identification of the eight-coordinated alkaline earth metal-dinitrogen complexes M(N) (M=Ca, Sr, Ba) possessing cubic (O) symmetry in a low-temperature neon matrix. The analysis of the electronic structure reveals that the metal-N bonds are mainly due to [M(d)]→(N) π backdonation, which explains the observed large red-shift in N-N stretching frequencies. The adducts M(N) have a triplet (A) electronic ground state and exhibit typical bonding features of transition metal complexes obeying the 18-electron rule. We also report the isolation and bonding analysis of the charged dinitrogen complexes [M(N)] (M=Ca, Sr).
我们报告了在低温氖基质中分离并通过光谱鉴定出具有立方（O）对称性的八配位碱土金属 - 二氮配合物M(N)₂（M = Ca、Sr、Ba）。电子结构分析表明，金属 - N键主要归因于[M(d)]→(N₂) π反馈键，这解释了观察到的N - N伸缩频率的大幅红移。加合物M(N)₂具有三重态（A）电子基态，并表现出遵循18电子规则的过渡金属配合物的典型键合特征。我们还报告了带电二氮配合物[M(N)₂]⁺（M = Ca、Sr）的分离和键合分析。
