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Phys Chem Chem Phys. 2019 Mar 28;21(12):6743-6749. doi: 10.1039/c8cp07748g. Epub 2019 Mar 12.

Infrared photodissociation spectroscopic investigation of TMO(CO)n+ (TM = Sc, Y, La): testing the 18-electron rule.

Author information

1
School of Chemical Science and Engineering, Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University, 1239 Siping Road, Shanghai, 200092, China. xfwang@tongji.edu.cn.
2
Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, 2005 Songhu Road, Shanghai 200438, China. gjwang@fudan.edu.cn.
3
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, P. R. China.

Abstract

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.

PMID:
30860207
DOI:
10.1039/c8cp07748g

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