A pendant proton shuttle on [Fe₄N(CO)₁₂]^- alters product selectivity in formate vs. H₂ production via the hydride [H-Fe₄N(CO)₁₂].

ABSTRACT: Proton relays are known to increase reaction rates for H₂ evolution and lower overpotentials in electrocatalytic reactions. In this report we describe two electrocatalysts, [Fe₄N(CO)₁₁(PPh₃)]^- (1^-) which has no proton relay, and hydroxyl-containing [Fe₄N(CO)₁₁(Ph₂P(CH₂)₂OH)]^- (2^-). Solid state structures indicate that these phosphine-substituted clusters are direct analogs of [Fe₄N(CO)₁₂]^- where one CO ligand has been replaced by a phosphine. We show that the proton relay changes the selectivity of reactions: CO₂ is reduced selectively to formate by 1^- in the absence of a re

SUBMITTER: Loewen ND 

PROVIDER: S-EPMC5477009 | biostudies-literature | 2016 Apr

REPOSITORIES: biostudies-literature