Wang Jia-Qi, Chi Chaoxian, Hu Han-Shi, Li Xiang, Luo Mingbiao, Li Jun, Zhou Mingfei
Department of Chemistry & Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, China.
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.
Angew Chem Int Ed Engl. 2020 Feb 3;59(6):2344-2348. doi: 10.1002/anie.201914536. Epub 2020 Jan 3.
Heteronuclear Group 3 metal/iron carbonyl anion complexes ScFe(CO) , YFe(CO) , and LaFe(CO) 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 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) 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.
通过气相法制备了异核第3族金属/铁羰基阴离子配合物ScFe(CO) 、YFe(CO) 和LaFe(CO) ，并采用质量选择红外（IR）光解离光谱以及量子化学计算对其进行了研究。所有这三种阴离子配合物的特征均为具有金属-金属键合的C平衡几何结构，所有三个羰基配体均与铁中心键合，且基态为闭壳单重态电子态。键合分析表明，裸第3族元素与Fe(CO) 片段之间存在多种键合相互作用。除了一个共价电子共享的金属-金属σ键和两个从Fe到第3族金属的配位π键外，还存在与与Fe键合的第3族原子和碳原子的额外多中心共价键。
