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

Wang, Chong1,4; Tian, Chang-Yi2,3; Zhao, Ya1; Jiang, Shuai1; Wang, Tiantong1,4; Zheng, Huijun1,4; Yan, Wenhui1,4; Li, Gang1; Xie, Hua1; Li, Jun2,3,5,6; Hu, Han-Shi2,3; Yang, Xueming1,5,6,7; Jiang, Ling1,7

2023-07-01

10.1002/anie.202305490

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

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.

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

SCI ; EI

英语

NI论文

其他

National Natural Science Foundation of China["22125303","92061203","21327901","22103082","22273101","22288201","22076095","22033005","22222605"] ; National Key Research and Development Program of China[2021YFA1400501] ; Youth Innovation Promotion Association of the Chinese Academy of Sciences (CAS)[2020187] ; Innovation Program for Quantum Science and Technology[2021ZD0303304] ; CAS[GJJSTD20220001] ; Dalian Institute of Chemical Physics (DICP)[DCLS201702] ; International Partnership Program of CAS[121421KYSB20170012] ; K. C. Wong Education Foundation[GJTD-2018-06]

Chemistry

Chemistry, Multidisciplinary

WOS:001030362100001

WILEY-V C H VERLAG GMBH

20232814369965

Carbonylation ; Chemical bonds ; Gases ; Ligands ; Molecular orbitals ; Ultraviolet spectroscopy

Metallurgy and Metallography:531 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Atomic and Molecular Physics:931.3

CHEMISTRY

Web of Science

1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
2.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
3.Tsinghua Univ, Engn Res Ctr Adv Rare Earth Mat, Minist Educ, Beijing 100084, Peoples R China
4.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
6.Southern Univ Sci & Technol, Shenzhen Key Lab Energy Chem, Shenzhen 518055, Peoples R China
7.Hefei Natl Lab, Hefei 230088, Peoples R China

Wang, Chong,Tian, Chang-Yi,Zhao, Ya,et al. Observation of Confinement-Free Neutral Group Three Transition Metal Carbonyls Sc(CO)(7) and TM(CO)(8) (TM=Y, La)[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2023,62.

Wang, Chong.,Tian, Chang-Yi.,Zhao, Ya.,Jiang, Shuai.,Wang, Tiantong.,...&Jiang, Ling.(2023).Observation of Confinement-Free Neutral Group Three Transition Metal Carbonyls Sc(CO)(7) and TM(CO)(8) (TM=Y, La).ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,62.

Wang, Chong,et al."Observation of Confinement-Free Neutral Group Three Transition Metal Carbonyls Sc(CO)(7) and TM(CO)(8) (TM=Y, La)".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 62(2023).