| Title | 2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins |
| Authors | Zheng, Yu Cao, Chang-Su Ma, Wangyang Chen, Tianyang Wu, Botao Yu, Chao Huang, Zhe Yin, Jianhao Hu, Han-Shi Li, Jun Zhang, Wen-Xiong Xi, Zhenfeng |
| Affiliation | Tsinghua Univ, Dept Chem, Minist Educ, Beijing 100084, Peoples R China Tsinghua Univ, Key Lab Organ Optoelect & Mol Engn, Minist Educ, Beijing 100084, Peoples R China Peking Univ, Beijing Natl Lab Mol Sci BNLMS, Minist Educ, Coll Chem,Key Lab Bioorgan Chem & Mol Engn, Beijing 100871, Peoples R China Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China |
| Keywords | STRUCTURAL-CHARACTERIZATION SANDWICH COMPLEXES MIXED-LIGAND CHEMISTRY METHYLIDENE REACTIVITY DIIODIDE CARBENE DIANION ALKYLIDENE |
| Issue Date | 17-Jun-2020 |
| Publisher | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY |
| Abstract | While reduction reactions are ubiquitous in chemistry, it is very challenging to further reduce electron-rich compounds, especially the anionic ones. In this work, the reduction of 1,3-butadienyl dianion, the anionic conjugated olefin, has been realized by divalent rare-earth metal compounds (SmI2), resulting in the formation of novel 2-butene tetraanion bridged disamarium(III) complexes. Density functional theory (DFT) analyses reveal two features: (i) the single electron transfer (SET) from 41 atomic orbitals (AOs) of each Sm center to the antibonding pi*-orbitals of 1,3-butadienyl dianion is feasible and the new HOMO formed by the bonding interaction between Sm Sd orbitals (AOs) and the pi*-orbitals of 1,3-butadienyl dianion can accept favorably 2e(-) from 4f AOs of Sm(II); (ii) the 2-butene tetraanionic ligand serves as a unique 10e(- )donating system, in which 4e(-) act as two sigma-donation bonding interactions while the rest 6e(-) as three pi-donation bonding interactions. The disamarium(III) complexes represent a unique class of the bridged bis-alkylidene rare-earth organometallic complexes. The ligand-based reductive reactivity of 2-butene tetraanion bridged disamarium(III) complexes demonstrates that 2-butene tetraanionic ligand serves as a 3e(-) reductant toward cyclooctatetraene (COT) to provide doubly COT-supported disamarabutadiene complexes. The reaction of the disamarium(III) complexes with Cp*Li produces the doubly Cp*-coordinated Sm(III) complexes via salt metathesis. In addition, the reaction with Mo(CO)(6) affords the oxycydopentadienyl dinuclear complex via CO insertion. |
| URI | http://hdl.handle.net/20.500.11897/590069 |
| ISSN | 0002-7863 |
| DOI | 10.1021/jacs.0c01690 |
| Indexed | SCI(E) |
| Appears in Collections: | å å¦ä¸ å å å·¥ç¨ å¦é ¢ 生物有机与分子工程教育部重点实验室 |
