Premium
An Iron(III) Dithiolene Complex as a Functional Model of Iron Hydrogenase
Author(s) -
Begum Ameerunisha,
Sarkar Sabyasachi
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100879
Subject(s) - chemistry , electrochemistry , protonation , hydrogenase , metal , glassy carbon , ferric , ferric ion , inorganic chemistry , carbon fibers , ion , electrode , crystallography , catalysis , cyclic voltammetry , organic chemistry , materials science , composite material , composite number
The iron(III) dithiolene complex [PPh 4 ] 2 [Fe(mnt) 2 (SPh)] ( 1 , mnt = maleonitrile dithiolate) has a highly distorted square‐pyramidal geometry and an intermediate spin ferric ion ( S Fe = 3/2), and catalyzes electrochemical H 2 evolution at the lowest achievable reduction potential known for iron‐containing electrocatalytic systems to date: E p = –0.309 V in CH 3 CN and E p = –0.53 V in water vs. Ag/AgCl using a modified glassy carbon working electrode. Control experiments suggest that the electrochemical H 2 evolution at low potential is promoted by metal‐assisted protonation at the S donors of the thiophenolato and mnt ligands, which liberate H 2 gas upon electrochemical reduction.