Electrochemistry of Germanium Porphyrins in Nonaqueous Media. Reactions of Water and Hydroxide Ligands Associated with (P)Ge(C1O4)2 and (P)Ge(OH)2, Where P Is the Dianion of Tetraphenylporphyrin (TPP) or Octaethylporphyrin (OEP)

K. M. Kadish; Q. Y. Xu; J. M. Barbe; J. E. Anderson; E. Wang; R. Guilard

doi:10.1021/ic00277a024

Electrochemistry of Germanium Porphyrins in Nonaqueous Media. Reactions of Water and Hydroxide Ligands Associated with (P)Ge(C1O₄)₂ and (P)Ge(OH)₂, Where P Is the Dianion of Tetraphenylporphyrin (TPP) or Octaethylporphyrin (OEP)

K. M. Kadish, Q. Y. Xu, J. M. Barbe, J. E. Anderson, E. Wang, R. Guilard

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

The electrochemistry of four germanium porphyrins was investigated in nonaqueous media. These compounds are represented as (P)Ge(X)₂ where P is the dianion of tetraphenylporphyrin (TPP) or octaethylporphyrin (OEP) and X is OH^- or ClO₄^-. The first one-electron oxidation of (P)Ge(ClO₄)₂ involves the porphyrin Π ring system while for (P)Ge(OH)₂ the abstraction of one electron occurs from a bound OH^- ligand and generates (P)Ge(ClO₄)(OH) as the porphyrin electrooxidation product. The addition of one or two electrons to (P)Ge(ClO₄)₂ results in an initial anion radical or dianion, but this species reacts with associated water that is in solution or is bound to the Ge(IV) complex, and this leads to the ultimate formation of (P)Ge(ClO₄)(OH) and (P)Ge(ClO₄)₂ as electroreduction products. Coulometric data as well as electrochemical, spectroelectrochemical, and ESR results are all self-consistent and are in good agreement with the proposed mechanism.

Original language	English (US)
Pages (from-to)	691-696
Number of pages	6
Journal	Inorganic Chemistry
Volume	27
Issue number	4
DOIs	https://doi.org/10.1021/ic00277a024
State	Published - Feb 1 1988
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Kadish, K. M., Xu, Q. Y., Barbe, J. M., Anderson, J. E., Wang, E., & Guilard, R. (1988). Electrochemistry of Germanium Porphyrins in Nonaqueous Media. Reactions of Water and Hydroxide Ligands Associated with (P)Ge(C1O₄)₂ and (P)Ge(OH)₂, Where P Is the Dianion of Tetraphenylporphyrin (TPP) or Octaethylporphyrin (OEP). Inorganic Chemistry, 27(4), 691-696. https://doi.org/10.1021/ic00277a024

Electrochemistry of Germanium Porphyrins in Nonaqueous Media. Reactions of Water and Hydroxide Ligands Associated with (P)Ge(C1O₄)₂ and (P)Ge(OH)₂, Where P Is the Dianion of Tetraphenylporphyrin (TPP) or Octaethylporphyrin (OEP). / Kadish, K. M.; Xu, Q. Y.; Barbe, J. M. et al.
In: Inorganic Chemistry, Vol. 27, No. 4, 01.02.1988, p. 691-696.

Research output: Contribution to journal › Article › peer-review

Kadish, KM, Xu, QY, Barbe, JM, Anderson, JE, Wang, E & Guilard, R 1988, 'Electrochemistry of Germanium Porphyrins in Nonaqueous Media. Reactions of Water and Hydroxide Ligands Associated with (P)Ge(C1O₄)₂ and (P)Ge(OH)₂, Where P Is the Dianion of Tetraphenylporphyrin (TPP) or Octaethylporphyrin (OEP)', Inorganic Chemistry, vol. 27, no. 4, pp. 691-696. https://doi.org/10.1021/ic00277a024

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title = "Electrochemistry of Germanium Porphyrins in Nonaqueous Media. Reactions of Water and Hydroxide Ligands Associated with (P)Ge(C1O4)2 and (P)Ge(OH)2, Where P Is the Dianion of Tetraphenylporphyrin (TPP) or Octaethylporphyrin (OEP)",

abstract = "The electrochemistry of four germanium porphyrins was investigated in nonaqueous media. These compounds are represented as (P)Ge(X)2 where P is the dianion of tetraphenylporphyrin (TPP) or octaethylporphyrin (OEP) and X is OH- or ClO4-. The first one-electron oxidation of (P)Ge(ClO4)2 involves the porphyrin Π ring system while for (P)Ge(OH)2 the abstraction of one electron occurs from a bound OH- ligand and generates (P)Ge(ClO4)(OH) as the porphyrin electrooxidation product. The addition of one or two electrons to (P)Ge(ClO4)2 results in an initial anion radical or dianion, but this species reacts with associated water that is in solution or is bound to the Ge(IV) complex, and this leads to the ultimate formation of (P)Ge(ClO4)(OH) and (P)Ge(ClO4)2 as electroreduction products. Coulometric data as well as electrochemical, spectroelectrochemical, and ESR results are all self-consistent and are in good agreement with the proposed mechanism.",

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N2 - The electrochemistry of four germanium porphyrins was investigated in nonaqueous media. These compounds are represented as (P)Ge(X)2 where P is the dianion of tetraphenylporphyrin (TPP) or octaethylporphyrin (OEP) and X is OH- or ClO4-. The first one-electron oxidation of (P)Ge(ClO4)2 involves the porphyrin Π ring system while for (P)Ge(OH)2 the abstraction of one electron occurs from a bound OH- ligand and generates (P)Ge(ClO4)(OH) as the porphyrin electrooxidation product. The addition of one or two electrons to (P)Ge(ClO4)2 results in an initial anion radical or dianion, but this species reacts with associated water that is in solution or is bound to the Ge(IV) complex, and this leads to the ultimate formation of (P)Ge(ClO4)(OH) and (P)Ge(ClO4)2 as electroreduction products. Coulometric data as well as electrochemical, spectroelectrochemical, and ESR results are all self-consistent and are in good agreement with the proposed mechanism.

AB - The electrochemistry of four germanium porphyrins was investigated in nonaqueous media. These compounds are represented as (P)Ge(X)2 where P is the dianion of tetraphenylporphyrin (TPP) or octaethylporphyrin (OEP) and X is OH- or ClO4-. The first one-electron oxidation of (P)Ge(ClO4)2 involves the porphyrin Π ring system while for (P)Ge(OH)2 the abstraction of one electron occurs from a bound OH- ligand and generates (P)Ge(ClO4)(OH) as the porphyrin electrooxidation product. The addition of one or two electrons to (P)Ge(ClO4)2 results in an initial anion radical or dianion, but this species reacts with associated water that is in solution or is bound to the Ge(IV) complex, and this leads to the ultimate formation of (P)Ge(ClO4)(OH) and (P)Ge(ClO4)2 as electroreduction products. Coulometric data as well as electrochemical, spectroelectrochemical, and ESR results are all self-consistent and are in good agreement with the proposed mechanism.

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