Temperature-dependent reduction pathways of complexes fac-[Re(CO)3(N-R-imidazole)(1,10-phenanthroline)+ (R = H, CH3)

被引：6

作者：

Zeng, Qiang ^{[1
]}

Messaoudani, Mahdi ^{[2
]}

Vlcek, Antonin, Jr. ^{[2
]}

Hartl, Frantisek ^{[1
]}

机构：

[1] Univ Reading, Dept Chem, Reading RG6 6AD, Berks, England

[2] Queen Mary Univ London, Sch Biol & Chem Sci, London E1 4NS, England

来源：

ELECTROCHIMICA ACTA | 2013年 / 110卷

关键词：

Rhenium carbonyl; Imidazole; Phenanthroline; Reductive bond cleavage; Reduction pathway; IR spectroelectrochemistry; N-ALKYLIMIDAZOLE LIGANDS; ELECTROCHEMICAL REDUCTION; ELECTRON; DYNAMICS; IR; SPECTROELECTROCHEMISTRY; TRYPTOPHAN; BIPYRIDINE; BEHAVIOR; OTF(-);

D O I：

10.1016/j.electacta.2013.02.018

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

Peculiar reduction pathways of the complexes fac-[Re(imH)(CO)(3)(phen)](+) and fac-[Re(imCH(3))(CO)(3) (phen)(+) (imH = imidazole, imCH(3) = 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(center dot-) -> imH intramolecular electron transfer coupled with N-H bond cleavage. This process is followed by second phen-localized 1e(-) reduction producing [Re-I(3-im(-))(CO)(3)(phen(center dot-))](-), similar to the analogous 2,2'-bipyridine complex. In contrast to the bpy analogue, the stability of the phen(center dot-)-containing complexes is significantly affected by lowering the temperature. At 233 K, a secondary reaction occurs in both [Re(3-im-)(CO)(3)(phen(center dot-))](-) and [Re(imCH(3))(CO)(3)(phen(center dot-))]. The resulting products exhibit nu(CO) wavenumbers indistinguishable from those of the parent phen(center dot-) complexes; however, their oxidation occurs at a considerably more positive electrode potential. It is-proposed that these species are produced by a new C-C bond formation between the C(2) site of 3-im(-) or imCH(3) and the C(2) site of the phen(center dot-) ligand. (C) 2013 Elsevier Ltd. All rights reserved.

引用

页码：702 / 708

页数：7

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