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A Combined “Electrochemical–Frustrated Lewis Pair” Approach to Hydrogen Activation: Surface Catalytic Effects at Platinum Electrodes
Author(s) -
Lawrence Elliot J.,
Blagg Robin J.,
Hughes David L.,
Ashley Andrew E.,
Wildgoose Gregory G.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404242
Subject(s) - electrochemistry , frustrated lewis pair , chemistry , catalysis , lewis acids and bases , borane , platinum , steric effects , redox , electron transfer , electrode , inorganic chemistry , photochemistry , stereochemistry , organic chemistry
Herein, we extend our “combined electrochemical–frustrated Lewis pair” approach to include Pt electrode surfaces for the first time. We found that the voltammetric response of an electrochemical–frustrated Lewis pair (FLP) system involving the B(C 6 F 5 ) 3 /[HB(C 6 F 5 ) 3 ] − redox couple exhibits a strong surface electrocatalytic effect at Pt electrodes. Using a combination of kinetic competition studies in the presence of a H atom scavenger, 6‐bromohexene, and by changing the steric bulk of the Lewis acid borane catalyst from B(C 6 F 5 ) 3 to B(C 6 Cl 5 ) 3 , the mechanism of electrochemical–FLP reactions on Pt surfaces was shown to be dominated by hydrogen‐atom transfer (HAT) between Pt, [PtH] adatoms and transient [HB(C 6 F 5 ) 3 ] ⋅ electrooxidation intermediates. These findings provide further insight into this new area of combining electrochemical and FLP reactions, and proffers additional avenues for exploration beyond energy generation, such as in electrosynthesis.