Wang Chen, Xiang Li, Yang Yan, Fang Jian, Maron Laurent, Leng Xuebing, Chen Yaofeng
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P.R. China.
Key Laboratory of Nonferrous Metal Chemistry, and Resources Utilization, Gansu Province School of Chemistry, and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P.R. China.
Chemistry. 2018 Apr 11;24(21):5637-5643. doi: 10.1002/chem.201706147. Epub 2018 Mar 9.
Alkylidene-bridged scandium-copper/silver heterobimetallic complexes were synthesized and structurally characterized. The complexes contain different Sc-C and M-C (M=Cu , Ag ) bonds. The reactivity of the scandium-copper heterobimetallic complex was also studied, which reveals that the heterobimetallic complex is a reaction intermediate for the transmetalation of akylidene group from Sc to Cu . The scandium-copper heterobimetallic complex also undergoes an addition reaction with CO, resulting in the formation of a new C=C double bond. DFT calculations were used to study the bonding and the subsequent reactivity with CO of the scandium-copper heterobimetallic complex. It clearly demonstrates a cooperative effect between the two metal centers through the formation of a direct Sc⋅⋅⋅Cu interaction that drives the reactivity with CO.
合成了亚烷基桥联的钪-铜/银异双金属配合物并对其进行了结构表征。这些配合物含有不同的Sc-C和M-C（M = Cu，Ag）键。还研究了钪-铜异双金属配合物的反应活性，结果表明该异双金属配合物是亚烷基从Sc转移至Cu的金属转移反应的中间体。钪-铜异双金属配合物还与CO发生加成反应，生成新的C = C双键。采用密度泛函理论（DFT）计算研究了钪-铜异双金属配合物的成键情况及其与CO的后续反应活性。结果清楚地表明，两个金属中心之间通过形成直接的Sc⋅⋅⋅Cu相互作用产生协同效应，从而驱动了与CO的反应活性。
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