Chloride-binding reactions and electrochemistry of (tetraphenylporphyrinato)cobalt and chloro(tetraphenylporphyrinato)cobalt in dichloromethane

Kadish, Karl M.; Lin, Xingguang; Han, Baocheng

doi:10.1021/ic00272a006

Cited by 75 publications

(54 citation statements)

References 11 publications

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“…1 shows the voltammograms for Co II (OEPone); similar voltammograms were obtained for Co II (OEPdione). This behavior has been seen for other Co(II) porphyrins [2] and [4], and is attributed to ligand exchange in Reaction (2). …”

Section: Visible Spectroelectrochemistry Of Cobalt Porphyrins and Porsupporting

confidence: 61%

“…Starting with Co(III) porphyrin complexes, the first two reductions (Co(III)/Co(II) and Co(II)/Co(I)) are predominantly metal centered [2], [3], [4] and [5]. The visible spectrum [6] and X-ray structure [7] of Co(I)TPP − have been obtained, and it has been shown to be a low spin complex.…”

Section: Introductionmentioning

confidence: 99%

“…The visible spectrum [6] and X-ray structure [7] of Co(I)TPP − have been obtained, and it has been shown to be a low spin complex. The visible spectroelectrochemistry of Co II (TPP) reduction was carried out by Kadish et al [2] and [3]. No studies of the spectroelectrochemical reduction of the Co(II)-alkyl substituted porphyrins have been reported.…”

Section: Introductionmentioning

confidence: 99%

“…In coordinating media, cobalt(II) is oxidized to cobalt(III) with either solvent or anionic coordination [2]. In non-coordinating media, the cobalt(II) π-cation radical is formed [14].…”

Section: Introductionmentioning

confidence: 99%

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Visible and infrared spectroelectrochemistry of cobalt porphinones and porphinediones

Tutunea¹

2012

Journal of Electroanalytical Chemistry

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Abstract:The visible and infrared spectroelectrochemistry of the redox chemistry of Co II -porphinone complexes were examined and compared with similar studies of the respective iron complexes. Cobalt(II) porphinone complexes undergo a one-electron reduction and two one-electron oxidations within the potential region that was studied in this work. The one electron spectroelectrochemical reduction of Co II (P) (P = octaethylporphyrin (OEP), octaethylporphinone (OEPone), and octaethylporphinedione (OEPdione)) were studied using visible spectroscopy, and their cobalt(I) complexes were characterized. The same reduction was examined by FTIR spectroscopy for P = OEPone and OEPdione. The infrared spectra showed downshifts of the νCO band that were consistent with a cobalt(I) complex and were similar to the iron(I) complex. The two one-electron oxidations of Co II (OEPone) and Co II (OEPdione) were also carried out using visible and infrared spectroelectrochemistry. The νCO band for cobalt was less sensitive to the metal oxidation state (III vs. II) than was observed in the iron complexes. VERSION; this is the author's final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation at the bottom of the page. NOT THE PUBLISHEDJournal of Electroanalytical Chemistry, Vol. 670 (April 1, 2012): pg. 16-22. DOI. This article is © Elsevier and permission has been granted for this version to appear in e-Publications@Marquette. Elsevier does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from Elsevier. 2Additional upshifts in the νCO band were observed for the π-cation radical. Isotopic 18 O substitution on the carbonyl group of the H2OEPone was done in order to determine the degree of mixing up the porphinone modes with the carbonyl vibrations.

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Section: Visible Spectroelectrochemistry Of Cobalt Porphyrins and Porsupporting

confidence: 61%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…In coordinating media, cobalt(II) is oxidized to cobalt(III) with either solvent or anionic coordination [2]. In non-coordinating media, the cobalt(II) π-cation radical is formed [14].…”

Section: Introductionmentioning

confidence: 99%

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Visible and infrared spectroelectrochemistry of cobalt porphinones and porphinediones

Tutunea¹

2012

Journal of Electroanalytical Chemistry

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“…Axially bonded nitrosyl [Co(TPP)] complexes have recently been reported [51,52]. It was observed that [Co(TPP)] undergoes reductive nitrosylation, but the reduction product is quite unstable and undergoes dissociative formation of cobalt(I) species [53][54][55][56]. Hence, in an analogous manner it is likely that the surface bound [Co(OBTTAP)] underwent reductive nitrosylation through a coordinated NO + (in acidic medium) or NO À 2 (in neutral medium) species [52,57].…”

Section: Cyclic Voltammetry In Non-aqueous Mediummentioning

confidence: 99%

Investigation of the electrochemical behavior of metallo-tetraazaporphyrin modified silver and pyrolytic graphite electrodes in aqueous nitrite solution

Prasad¹,

Kumar²

2005

Journal of Electroanalytical Chemistry

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Electrochemistry of Metalloporphyrin Homo- and Hetero-dimers Containing Co, Ni or Cu Metal Ions

Kadish

Guo

Caemelbecke

et al. 1998

J. Porphyrins Phthalocyanines

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The synthesis and electrochemical characterization of five covalently linked symmetrical and unsymmetrical metalloporphyrin dimers containing tetraphenylporphyrin (TPP), triphenylporphyrin (TriPP) or diethylhexamethylporphyrin (DEHMP) macrocycles are reported. The investigated compounds are represented as M(TPP-DEHMP)M ( M = Co , Ni , Cu ) and M(TPP-TriPP)M ( M = Ni , Cu ), where TPP-DEHMP and TPP-TriPP are the tetraanions of 1-[5-(10,15,20-triphenylporphyrinyl)]-4-[10-(2,18-diethyl-3,7,8,12,13,17-hexamethylporphyrinyl)]benzene and 1,4-bis-[5″-(10″,15″,20″-triphenylporphy-rinyl)]benzene respectively. The UV-vis spectra of the neutral dimers can be simply obtained by superimposing the spectra of the two corresponding monomeric (TPP)M and (DEHMP)M units, the latter of which is approximated by (OEP)M (TPP and OEP are the dianions of tetraphenylporphyrin and octaethylporphyrin respectively). The reduction potentials of the dimeric porphyrins are similar to those of the combined individual monomeric units. This is also the case for all oxidations of M(TPP-TriPP)M as well as the first TPP- and DEHMP-centered oxidations of M(TPP-DEHMP)M to give porphyrin π-cation radicals. However, the second DEHMP macrocycle-centered oxidations of M(TPP-DEHMP)M to give porphyrin dications occur at half-wave potentials which are 50-100 mV easier than E1/2 for the same ring-centered oxidations of the corresponding (OEP)M monomers. The electrochemical data indicate that there is an electronic interaction between the (TPP)M and (DEHMP)M units of M(TPP-DEHMP)M only under conditions where both macrocycles of the dimer have been converted to a porphyrin π-cation radical.

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Chloride-binding reactions and electrochemistry of (tetraphenylporphyrinato)cobalt and chloro(tetraphenylporphyrinato)cobalt in dichloromethane

Cited by 75 publications

References 11 publications

Visible and infrared spectroelectrochemistry of cobalt porphinones and porphinediones

Visible and infrared spectroelectrochemistry of cobalt porphinones and porphinediones

Investigation of the electrochemical behavior of metallo-tetraazaporphyrin modified silver and pyrolytic graphite electrodes in aqueous nitrite solution

Electrochemistry of Metalloporphyrin Homo- and Hetero-dimers Containing Co, Ni or Cu Metal Ions

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