Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 11, Pages 4267-4271Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201406609
Keywords
boranes; density functional calculations; radical anions; substituent effect; torsion angles
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Funding
- MEXT [26288019, 25287091, 24109012, 24109008]
- Science Research Promotion Fund
- Asahi Glass Foundation
- Research Grants Council of Hong Kong [HKUST 603313, CUHK7/CRF/12G]
- Grants-in-Aid for Scientific Research [24109008, 24109012, 25287091, 26288019] Funding Source: KAKEN
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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.
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