Observation of Confinement-Free Neutral Group Three Transition Metal Carbonyls Sc(CO)7 and TM(CO)8 (TM=Y, La)

Chong Wang; Chang-Yi Tian; Ya Zhao; Shuai Jiang; Tiantong Wang; Huijun Zheng; Wenhui Yan; Gang Li; Hua Xie; Jun Li; Han-Shi Hu; Xueming Yang; Ling Jiang

doi:10.1002/anie.202305490

Observation of Confinement-Free Neutral Group Three Transition Metal Carbonyls Sc(CO)₇ and TM(CO)₈ (TM=Y, La)

Angew Chem Int Ed Engl. 2023 Aug 7;62(32):e202305490. doi: 10.1002/anie.202305490. Epub 2023 Jul 4.

Authors

Chong Wang^{1

2}, Chang-Yi Tian³, Ya Zhao¹, Shuai Jiang¹, Tiantong Wang^{1

2}, Huijun Zheng^{1

2}, Wenhui Yan^{1

2}, Gang Li¹, Hua Xie¹, Jun Li^{3

4}, Han-Shi Hu³, Xueming Yang^{1

4

5}, Ling Jiang^{1

5}

Affiliations

¹ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China.
² University of Chinese Academy of Sciences, 100049, Beijing, China.
³ Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, 100084, Beijing, China.
⁴ Department of Chemistry and Shenzhen Key Laboratory of Energy Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China.
⁵ Hefei National Laboratory, 230088, Hefei, China.

PMID: 37340827
DOI: 10.1002/anie.202305490

Abstract

Spectroscopic characterization of neutral highly-coordinated compounds is essential in fundamental and applied research, but has been proven to be a challenging experimental target because of the difficulty in mass selection. Here, we report the preparation and size-specific infrared-vacuum ultraviolet (IR-VUV) spectroscopic identification of group-3 transition metal carbonyls Sc(CO)₇ and TM(CO)₈ (TM=Y, La) in the gas phase, which are the first confinement-free neutral heptacarbonyl and octacarbonyl complexes. The results indicate that Sc(CO)₇ has a C_2v structure and TM(CO)₈ (TM=Y, La) have a D_4h structure. Theoretical calculations predict that the formation of Sc(CO)₇ and TM(CO)₈ (TM=Y, La) is both thermodynamically exothermic and kinetically facile in the gas phase. These highly-coordinated carbonyls are 17-electron complexes when only those valence electrons that occupy metal-CO bonding orbitals are considered, in which the ligand-only 4b_1u molecular orbital is ignored. This work opens new avenues toward the design and chemical control of a large variety of compounds with unique structures and properties.

Keywords: Carbonyl Complexes; Group 3 Metals; Infrared-Vacuum Ultraviolet Spectroscopy; Metal-Ligand Bonding; Quantum Chemical Calculation.

Abstract

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