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Electrochemical Reductive Deprotonation of an Imidazole Ligand in a Bipyridine Tricarbonyl Rhenium(I) Complex
Author(s) -
Zeng Qiang,
Messaoudani Mahdi,
Vlček Antonín,
Hartl František
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.201101100
Subject(s) - chemistry , deprotonation , imidazole , rhenium , ligand (biochemistry) , imidazolate , intramolecular force , electron transfer , photochemistry , electrochemistry , bipyridine , iridium , medicinal chemistry , inorganic chemistry , stereochemistry , crystallography , organic chemistry , catalysis , electrode , crystal structure , ion , biochemistry , receptor
The reduction pathway of fac ‐[Re I (imH)(CO) 3 (bpy)] + was studied in situ by UV/Vis/NIR–IR spectroelectrochemistry with an OTTLE cell. The complex underwent 1e – reduction of the 2,2′‐bipyridine (bpy) ligand and intramolecular electron transfer, which resulted in the conversion of the axial imidazole (imH) ligand to 3‐imidazolate (3‐im – ). This step was followed by two bpy‐based 1e – reductions to ultimately produce five‐coordinate [Re(CO) 3 (bpy)] – and free 3‐im – . The identity of the reduction product fac ‐[Re(3‐im – )(CO) 3 (bpy)] has been proven by partial chemical deprotonation of the parent complex followed by IR spectroelectrochemistry. This is the first time that the reductive electrochemical conversion of metal‐coordinated imidazole to terminal 3‐imidazolate has been observed.