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)

We have clarified and observed the high electron affinity of pinBBMes2 (1; Mes=mesityl, pin=pinacolato). By using electrochemistry, it was shown that 1 has a higher electron affinity than those of B2pin2 and Mes3B. 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 BB 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.