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2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins
- Source :
- Journal of the American Chemical Society. 142(24)
- Publication Year :
- 2020
-
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 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) the 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 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 oxycyclopentadienyl dinuclear complex via CO insertion.
- Subjects :
- Ligand
chemistry.chemical_element
General Chemistry
Conjugated system
010402 general chemistry
Metathesis
Antibonding molecular orbital
01 natural sciences
Biochemistry
Catalysis
0104 chemical sciences
Samarium
Cyclooctatetraene
chemistry.chemical_compound
Crystallography
Colloid and Surface Chemistry
chemistry
Density functional theory
Reactivity (chemistry)
Subjects
Details
- ISSN :
- 15205126
- Volume :
- 142
- Issue :
- 24
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi.dedup.....408bf50c26614070914aa623f3d620a0