Lowering the Reduction Potential of a Boron Compound by Means of the Substituent Effect of the Boryl Group: One-Electron Reduction of an Unsymmetrical Diborane(4)

被引：45

作者：

Asakawa, Hiroki ^{[1
]}

Lee, Ka-Ho ^{[2
]}

Furukawa, Ko ^{[3
]}

Lin, Zhenyang ^{[2
]}

Yamashita, Makoto ^{[1
]}

机构：

[1] Chuo Univ, Dept Appl Chem, Fac Sci & Engn, Bunkyo Ku, Tokyo 1128551, Japan

[2] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China

[3] Niigata Univ, Inst Res Promot, Ctr Instrumental Anal, Nishi Ku, 8050 Ikarashi 2 No Cho, Niigata 9502181, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2015年 / 21卷 / 11期

关键词：

boranes; density functional calculations; radical anions; substituent effect; torsion angles; RADICAL-ANION; X-RAY; REACTIVITY; COMPLEXES; CHEMISTRY; BORYLLITHIUM; FORM; GENERATION; MOIETIES; BORANES;

D O I：

10.1002/chem.201406609

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We have clarified and observed the high electron affinity of pinB-BMes(2) (1; Mes = mesityl, pin = pinacolato). By using electrochemistry, it was shown that 1 has a higher electron affinity than those of B(2)pin(2) and Mes(3)B. One-electron reduction of 1 gave the corresponding radical anion. The ESR spectroscopy and DFT calculation revealed the unsymmetrical distribution of electron density over the B-B bond. UV/Vis spectroscopy showed that the SOMO-related absorption supports the deep purple color of the radical anion. DFT studies on the torsion angle dependency of the LUMO levels and relative energies revealed the reason why 1 has high electron affinity as a result of the substituent effect of the Bpin group.

引用

页码：4267 / 4271

页数：5

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