CATALYSIS OF ELECTROCHEMICAL REDUCTION OF WEAK ACIDS TO PRODUCE H(2): ROLE OF O-H center dot center dot center dot S HYDROGEN BONDING

作者：Chen Jinzhu; Vannucci Aaron K; Mebi Charles A; Okumura Noriko; Borowski Susan C; Lockett L Tori; Swenson Matthew; Lichtenberger Dennis L; Evans Dennis H; Glass Richard S^*

来源：Phosphorus, Sulfur, and Silicon and the Related Elements, 2011, 186(5): 1288-1292.

DOI：10.1080/10426507.2010.523035

• Hydrogen bonding
• hydrogen production
• hydroquinone

The role of intramolecular OH center dot center dot center dot S hydrogen bonding in the electrochemical reduction of protons from acetic acid using biomimetically inspired catalysts has been studied. The catalysts, hydroquinone moieties annulated to an Fe(2)S(2)(CO)(6) core, were synthesized by piperidine-mediated conjugate addition of the dithiol Fe(2)(SH)(2)(CO)(6) to quinones in 26-76% yields. These complexes catalyze electrochemical H(2) production from acetic acid. Evidence for weak intramolecular OH center dot center dot center dot S hydrogen bonding in the neutral complexes is presented. Such hydrogen bonding becomes stronger as the charge increases on the sulfur in the electrochemically produced dianions due to "charge assistance," and this has chemical consequences.

• 出版日期2011