Generation of pyridyl coordinated organosilicon cation pool by oxidative Si-Si bond dissociation

• Toshiki Nokami,
• Ryoji Soma,
• Yoshimasa Yamamoto,
• Toshiyuki Kamei,
• Kenichiro Itami and
• Jun-ichi Yoshida

Beilstein J. Org. Chem. 2007, 3, No. 7, doi:10.1186/1860-5397-3-7

• the silicon atom. Eventually, Bu4NB(C6F5)4 was found to be an appropriate supporting electrolyte to generate and accumulate the organosilicon cation 3d. The 1H NMR spectrum of the solution obtained by the electrochemical oxidation of 1d in CH2Cl2 (containing 10% CD2Cl2) using Bu4NB(C6F5)4 at 0°C

• more effective than the 2-pyridylethyl group. The intramolecular coordination in the radical cation is supported by the DFT calculations as shown in Figure 2. It is also important to note that such coordination elongates the Si-Si bond and facilitates its dissociation. Preparative electrochemical

• oxidation of 1d was carried out to generate and accumulate the corresponding organosilicon cation 3d (Scheme 3). Nature of the counter anion was very important. When 1d was oxidized in the presence of Bu4NBF4, which is a common supporting electrolyte for the "cation pool" method, fluoride was introduced on