Infrared photodissociation spectroscopic investigation of TMO(CO)n+ (TM = Sc, Y, La): testing the 18-electron rule
Infrared photodissociation spectroscopic investigation of TMO(CO)n+ (TM = Sc, Y, La): testing the 18-electron rule
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TMO(CO)(n)( ) (TM = Sc, Y, La) 的红外光解光谱研究：测试 18 电子规则
DOI：
10.1039/c8cp07748g
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发表时间：
2019-03-28
影响因子：
3.3
通讯作者：
Wang, Guanjun
中科院分区：
文献类型：
--
作者：
Chen, Yinjuan;Xin, Ke;Wang, Guanjun
对激光蒸发法制备的气态TMO(CO)(N)(+)(Tm=Sc，Y，La)络阳离子进行了质量选择和C-O伸缩频段的红外光解离光谱研究。用密度泛函理论计算了它们的结构和振动频率，支持和解释了实验结果。CO配体对SCO(CO)(N)(+)、YO(CO)(N)(+)和LaO(CO)(N)(+)的饱和配位数分别为6、7和9，即合成了18、20和24电子气态阳离子配合物。根据我们对电子结构的分析，YO(CO)(7)(+)络合物也遵循18电子规则，因为其中一个占据的价分子轨道只由配体轨道形成。LaO(CO)(9)(+)中4f轨道的贡献与其与24电子价层的高配位数有关。
Gaseous TMO(CO)(n)(+) (TM = Sc, Y, La) complex cations prepared via laser vaporization were mass-selected and studied by infrared photodissociation spectroscopy in the C-O stretching frequency region. The structures and vibrational frequencies were calculated by density functional theory to support and interpret the experimental results. The saturated coordination number of CO ligands for ScO(CO)(n)(+), YO(CO)(n)(+) and LaO(CO)(n)(+) was demonstrated to be six, seven and nine, respectively, namely, the nominal 18-, 20- and 24-electron gaseous cation complexes were synthesized. Based on our analysis of the electronic structure, the YO(CO)(7)(+) complex also obeys the 18-electron rule, since one of the occupied valence molecular orbitals is formed only by ligand orbitals. The contribution of 4f orbitals in LaO(CO)(9)(+) accounts for its high coordination number with a 24-electron valence shell.