Electrochemistry of nickel and copper beta-octahalogeno-meso-tetraarylporphyrins. Evidence for important role played by saddling-induced metal(d(x2)-(y2))-porphyrin("a(2u)") orbital interactions

Citation
A. Ghosh et al., Electrochemistry of nickel and copper beta-octahalogeno-meso-tetraarylporphyrins. Evidence for important role played by saddling-induced metal(d(x2)-(y2))-porphyrin("a(2u)") orbital interactions, J PHYS CH B, 105(34), 2001, pp. 8120-8124
Citations number
36
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY B
ISSN journal
1520-6106 → ACNP
Volume
105
Issue
34
Year of publication
2001
Pages
8120 - 8124
Database
ISI
SICI code
1520-6106(20010830)105:34<8120:EONACB>2.0.ZU;2-H
Abstract
This is an electrochemical study of the Ni(II) and Cu(II) complexes of a se ries of beta -octahalogeno-meso-tetrakis(p-X-phenyl)porphyrins, M[Y8T(p-X-P )P] (M = Ni, Cu; Y = Cl, Br; X = CH3, H, F, Br, COOMe, CF3, NO2). We have a nalyzed the oxidation and reduction potentials by means of the Hammett equa tion. The Ni and Cu series exhibit significant differences in electrochemic al behavior in terms of the absolute values of the redox potentials and sub stituent effects. DFT calculations suggest that these differences may be as cribed to differences in saddling-induced metal(d(x2-y2))-porphyrin(a(2u)) orbital interaction between the Ni and Cu porphyrins.