Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
6615825 | Electrochimica Acta | 2013 | 7 Pages |
Abstract
Peculiar reduction pathways of the complexes fac-[Re(imH)(CO)3(phen)]+ and fac-[Re(imCH3)(CO)3(phen)]+ (imH = imidazole, imCH3 = N-methylimidazole and phen = 1,10-phenanthroline) have been unravelled by performing combined cyclic voltammetric and in situ IR spectroelectrochemical experiments. In the temperature range of 293-233 K, the initial reduction of the phen ligand in [Re(imH)(CO)3(phen)]+ results in irreversible conversion of the imidazole ligand to 3-imidazolate by a rapid phen
- â â imH intramolecular electron transfer coupled with NH bond cleavage. This process is followed by second phen-localized 1eâ reduction producing [ReI(3-imâ)(CO)3(phen
- â)]â, similar to the analogous 2,2â²-bipyridine complex. In contrast to the bpy analogue, the stability of the phen
- â-containing complexes is significantly affected by lowering the temperature. At 233Â K, a secondary reaction occurs in both [Re(3-imâ)(CO)3(phen
- â)]â and [Re(imCH3)(CO)3(phen
- â)]. The resulting products exhibit ν(CO) wavenumbers indistinguishable from those of the parent phen
- â complexes; however, their oxidation occurs at a considerably more positive electrode potential. It is proposed that these species are produced by a new CC bond formation between the C(2) site of 3-imâ or imCH3 and the C(2) site of the phen
- â ligand.
- â â imH intramolecular electron transfer coupled with NH bond cleavage. This process is followed by second phen-localized 1eâ reduction producing [ReI(3-imâ)(CO)3(phen
- â)]â, similar to the analogous 2,2â²-bipyridine complex. In contrast to the bpy analogue, the stability of the phen
- â-containing complexes is significantly affected by lowering the temperature. At 233Â K, a secondary reaction occurs in both [Re(3-imâ)(CO)3(phen
- â)]â and [Re(imCH3)(CO)3(phen
- â)]. The resulting products exhibit ν(CO) wavenumbers indistinguishable from those of the parent phen
- â complexes; however, their oxidation occurs at a considerably more positive electrode potential. It is proposed that these species are produced by a new CC bond formation between the C(2) site of 3-imâ or imCH3 and the C(2) site of the phen
- â ligand.
Related Topics
Physical Sciences and Engineering
Chemical Engineering
Chemical Engineering (General)
Authors
Qiang Zeng, Mahdi Messaoudani, AntonÃn Jr., FrantiÅ¡ek Hartl,