Multiple Bonding Between Group 3 Metals and Fe(CO)3

Jia-Qi Wang; Chaoxian Chi; Han-Shi Hu; Xiang Li; Mingbiao Luo; Jun Li; Mingfei Zhou

doi:10.1002/anie.201914536

Multiple Bonding Between Group 3 Metals and Fe(CO)₃

Angew Chem Int Ed Engl. 2020 Feb 3;59(6):2344-2348. doi: 10.1002/anie.201914536. Epub 2020 Jan 3.

Authors

Jia-Qi Wang¹, Chaoxian Chi², Han-Shi Hu¹, Xiang Li¹, Mingbiao Luo², Jun Li^{1

3}, Mingfei Zhou⁴

Affiliations

¹ Department of Chemistry & Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, China.
² School of Chemistry, Biological and Materials Sciences, Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China University of Technology, Nanchang, Jiangxi Province, 330013, China.
³ Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
⁴ Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China.

PMID: 31769913
DOI: 10.1002/anie.201914536

Abstract

Heteronuclear Group 3 metal/iron carbonyl anion complexes ScFe(CO)₃ ^- , YFe(CO)₃ ^- , and LaFe(CO)₃ ^- are prepared in the gas phase and studied by mass-selective infrared (IR) photodissociation spectroscopy as well as quantum-chemical calculations. All three anion complexes are characterized to have a metal-metal-bonded C_3v equilibrium geometry with all three carbonyl ligands bonded to the iron center and a closed-shell singlet electronic ground state. Bonding analyses reveal that there are multiple bonding interactions between the bare group-3 elements and the Fe(CO)₃ ^- fragment. Besides one covalent electron-sharing metal-metal σ bond and two dative π bonds from Fe to the Group 3 metal, there is additional multicenter covalent bonding with the Group 3 atom bonded to Fe and the carbon atoms.

Keywords: group-3 metals; infrared photodissociation spectroscopy; iron; metal-metal bonds; quantum-chemical studies.

Abstract

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