Dianionic Carbon-Bridged Scandium-Copper/Silver Heterobimetallic Complexes: Synthesis, Bonding, and Reactivity

Chen Wang; Li Xiang; Yan Yang; Jian Fang; Laurent Maron; Xuebing Leng; Yaofeng Chen

doi:10.1002/chem.201706147

Dianionic Carbon-Bridged Scandium-Copper/Silver Heterobimetallic Complexes: Synthesis, Bonding, and Reactivity

Chemistry. 2018 Apr 11;24(21):5637-5643. doi: 10.1002/chem.201706147. Epub 2018 Mar 9.

Authors

Chen Wang¹, Li Xiang¹, Yan Yang², Jian Fang², Laurent Maron³, Xuebing Leng¹, Yaofeng Chen¹

Affiliations

¹ 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.
² Key Laboratory of Nonferrous Metal Chemistry, and Resources Utilization, Gansu Province School of Chemistry, and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P.R. China.
³ LPCNO, CNRS & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077, Toulouse, France.

PMID: 29411911
DOI: 10.1002/chem.201706147

Abstract

Alkylidene-bridged scandium-copper/silver heterobimetallic complexes were synthesized and structurally characterized. The complexes contain different Sc-C and M-C (M=Cu^I , Ag^I ) 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^III to Cu^I . 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.

Keywords: alkylidenes; cooperative effects; density functional calculations; heterometallic; scandium.