Observation of alkaline earthcomplexes M(CO)8 (M = Ca, Sr, or Ba)that mimic transition metals
Xuan Wu,1+Lili Zhao,2+, Jiaye Jin,1Sudip Pan,2Wei Li,1Xiaoyang Jin,1Guanjun Wang,1Mingfei Zhou1* and Gernot Frenking2,3*
1Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, China.
2Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 211816, China
3Fachbereich Chemie, Philipps-Universitat Marburg, Hans-Meerwein-Strasse, D-35043 Marburg, Germany
Abstract: The alkaline earth atoms calcium, strontium and barium are known as classical main-group elements, which use their (n)sand (n)pvalence orbitals for chemical bonding. We report the isolation and spectroscopic identification of the eight-coordinated carbonyl complexes AE(CO)8(AE = Ca, Sr, Ba) possessing cubic (Oh) symmetry in a low-temperature matrix. The analysis of the electronic structure reveals that the metal-CO bonds are mainly due to [AE(dπ)]→(CO)8π backdonation, which explains the strong red-shift of the C-O stretching frequencies. The complexes AE(CO)8exhibit typical features of transition metal complexes obeying the 18-electron rule.
Science, 2018, 361, 912-916. 2017年影响因子：37.205
论文链接:http://science.sciencemag.org/content/361/6405/912
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