2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins
- 14 May 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (24), 10705-10714
- https://doi.org/10.1021/jacs.0c01690
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 di-samarium(III) complexes. Density functional theory (DFT) analyses reveal two features: i) the single electron transfer (SET) from 4f atomic orbitals (AOs) of each Sm center to the antibonding π*-orbitals of 1,3-butadienyl dianion is feasible, and the new HOMO formed by the bonding interaction between Sm 5d orbitals (AOs) and the π*-orbitals of 1,3-butadienyl dianion can accept favorably 2e- from 4f AOs of Sm(II); ii) 2-butene tetraanionic ligand serves as a unique 10e- donating system, in which 4e- act as two σ-donation bonding interactions while the rest 6e- as three π-donation bonding interactions. The di-samarium(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 di-samarium(III) complexes demonstrates that 2-butene tetraanionic ligand serves as a 3e- reductant toward cyclooctatetraene (COT) to provide doubly COT-supported di-samarabutadiene complexes. The reaction of the di-samarium(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 oxycyclopentadienyl dinuclear complex via CO insertion.Keywords
Funding Information
- China Postdoctoral Science Foundation (2018M641062)
- National Natural Science Foundation of China (21590792, 21725201, 21890721)
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