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A Model for the Prediction of the Redox Potentials in [FeFe]‐Clusters from the Electronic Properties of Isocyanide Ligands
Author(s) -
Collado Alba,
Torres Alejandro,
GómezGallego Mar,
Casarrubios Luis,
Sierra Miguel A.
Publication year - 2020
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202001820
Subject(s) - isocyanide , substituent , electrochemistry , ligand (biochemistry) , redox , chemistry , homo/lumo , metal , electronic effect , electronic structure , photochemistry , computational chemistry , molecule , inorganic chemistry , electrode , stereochemistry , organic chemistry , biochemistry , receptor , steric effects
Using an experimental‐computational methodology, arylisocyanides (CNAr) have shown to be excellent probes to study the effect of electronic properties in the electrochemical behavior of [FeFe]‐complexes. The calculated LUMO distribution of p‐ substituted [Fe 2 {(μ‐SCH 2 ) 2 N t Bu}(CO) 5 (CNAr)] complexes ( 2 ) show that, depending on the substituent, the first reduction event ( E pc ) may be metal centered or ligand centered. The electrochemical response of complexes 2 has been experimentally studied and correlated to the calculations performed. The E pc values were found to directly correlate to different spectroscopic properties such as IR and 13 C{ 1 H} NMR spectroscopies. These findings could be used to predict the E pc values of new [FeFe]‐complexes.