Zhao Jie, Ji Ting, Xiao Xin, Wang Xuefeng, Beckers Helmut, Riedel Sebastian
Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, China.
School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China.
Inorg Chem. 2020 Oct 5;59(19):14355-14366. doi: 10.1021/acs.inorgchem.0c02132. Epub 2020 Sep 25.
Matrix isolation infrared spectroscopy combined with quantum-chemical calculations were employed to study the reactions of calcium atoms with silane, germane, and stannane in a 4 K argon matrix. The ion pairs [HCa] and [EH] (E = Si, Ge, and Sn) in both the classical structure HCaEH and the bridged structure HCa(μ-H)E were identified based on the H/D isotopic substitution experiments and quantum-chemical calculations. The results show that the reaction between ground-state Ca and EH proceeds inefficiently, and only after the photolytic activation of Ca atoms to the Ca(P:44) state does insertion occur to give HCaEH, which rearranges to HCa(μ-H)E upon photolysis. Topological analysis of the electronic structure suggests that the nonclassical structure HCa(μ-H)E is formed by the electrostatic interaction with charge-inverted hydrogen bridge bond, while HCaEH is dominated by (HCa)(EH) ion pair interactions.
