2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins

Zheng，Yu1; Cao，Chang Su2; Ma，Wangyang1; Chen，Tianyang1; Wu，Botao1; Yu，Chao1; Huang，Zhe1; Yin，Jianhao1; Hu，Han Shi2; Li，Jun2,3; Zhang，Wen Xiong1; Xi，Zhenfeng1

2020-06-17

10.1021/jacs.0c01690

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

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.

SCI ; EI

英语

NI论文

其他

National Natural Science Foundation of China[21725201][21890721][21590792] ; China Postdoctoral Science Foundation[2018M641062]

Chemistry

Chemistry, Multidisciplinary

WOS:000542929600015

AMER CHEMICAL SOC

20202708887915

Olefins ; Rare earths ; Chemical bonds ; Electrons ; Samarium compounds ; Density functional theory ; Reduction ; Orbits ; Organometallics

Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

2-s2.0-85086626255

Scopus

1.Beijing National Laboratory for Molecular Sciences (BNLMS),Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,College of Chemistry,Peking University,100871,China
2.Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education,Tsinghua University,100084,China
3.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China

Zheng，Yu,Cao，Chang Su,Ma，Wangyang,et al. 2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins[J]. Journal of the American Chemical Society,2020,142(24):10705-10714.

Zheng，Yu.,Cao，Chang Su.,Ma，Wangyang.,Chen，Tianyang.,Wu，Botao.,...&Xi，Zhenfeng.(2020).2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins.Journal of the American Chemical Society,142(24),10705-10714.

Zheng，Yu,et al."2-Butene Tetraanion Bridged Dinuclear Samarium(III) Complexes via Sm(II)-Mediated Reduction of Electron-Rich Olefins".Journal of the American Chemical Society 142.24(2020):10705-10714.