Synthesis and Reactivity of σ-Bonded Silicon Metalloporphyrins. Spectroscopic Characterization and Electrochemistry of (P)Si(R)2, (P)Si(R)X, and (P)SiX2, Where R = C6H5 or CH3 and X = OH- or ClO4-

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

doi:10.1021/ic00280a020

Synthesis and Reactivity of σ-Bonded Silicon Metalloporphyrins. Spectroscopic Characterization and Electrochemistry of (P)Si(R)₂, (P)Si(R)X, and (P)SiX₂, Where R = C₆H₅ or CH₃ and X = OH^- or ClO₄^-

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

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

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Abstract

The synthesis, characterization, and electrochemistry of several (OEP)Si(R)₂, (OEP)Si(R)_X, and (OEP)SiX₂ complexes are reported, where OEP is the dianion of octaethylporphyrin, R is C6H₅ or CH₃, and X = C1O_4^- or OH^- (OEP)Si(C₆H₅)2 can be converted to (OEP)Si(C₆H₅)OH in CHCl₃ by irradiation with visible light in the absence of oxygen. Each Si(IV) complex undergoesa reversible electroreduction at theporphyrin ring system. In contrast,the initial electrooxidations of these complexes are irreversible and theoverall processes involve one or more coupled chemical reactions following electron transfer. (OEP)Si-(C₆H₅)₂ can be converted to (OEP)Si(C₆H₅)OH after oxidation by one electron while further oxidation generates (OEP)Si-(C₆H₅)ClO₄. The latter compound can also be formed by reaction of (OEP)Si(C₆H₅)₂ with 2 equiv of HClO₄ in Ph CN.(OEP)Si(CH₃)₂ undergoes electrochemistry different from that of (OEP)Si(C₆H₅)₂ and gives (OEP)Si(CH₃)ClO₄ and (OEP)-Si(ClO₄)₂ as successive electrooxidation products. An overall oxidation/reduction scheme for (OEP)Si(R)₂ is presented and compared to mechanisms for oxidation/reduction of (OEP)Si(R)X and (OEP)SiX₂.

Original language	English (US)
Pages (from-to)	1191-1198
Number of pages	8
Journal	Inorganic Chemistry
Volume	27
Issue number	7
DOIs	https://doi.org/10.1021/ic00280a020
State	Published - Apr 1 1988
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Synthesis and Reactivity of σ-Bonded Silicon Metalloporphyrins. Spectroscopic Characterization and Electrochemistry of (P)Si(R)₂, (P)Si(R)X, and (P)SiX₂, Where R = C₆H₅ or CH₃ and X = OH^- or ClO₄^-. / Kadish, K. M.; Xu, Q. Y.; Barbe, J. M. et al.
In: Inorganic Chemistry, Vol. 27, No. 7, 01.04.1988, p. 1191-1198.

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

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title = "Synthesis and Reactivity of σ-Bonded Silicon Metalloporphyrins. Spectroscopic Characterization and Electrochemistry of (P)Si(R)2, (P)Si(R)X, and (P)SiX2, Where R = C6H5 or CH3 and X = OH- or ClO4-",

abstract = "The synthesis, characterization, and electrochemistry of several (OEP)Si(R)2, (OEP)Si(R)X, and (OEP)SiX2 complexes are reported, where OEP is the dianion of octaethylporphyrin, R is C6H5 or CH3, and X = C1O4- or OH- (OEP)Si(C6H5)2 can be converted to (OEP)Si(C6H5)OH in CHCl3 by irradiation with visible light in the absence of oxygen. Each Si(IV) complex undergoesa reversible electroreduction at theporphyrin ring system. In contrast,the initial electrooxidations of these complexes are irreversible and theoverall processes involve one or more coupled chemical reactions following electron transfer. (OEP)Si-(C6H5)2 can be converted to (OEP)Si(C6H5)OH after oxidation by one electron while further oxidation generates (OEP)Si-(C6H5)ClO4. The latter compound can also be formed by reaction of (OEP)Si(C6H5)2 with 2 equiv of HClO4 in Ph CN.(OEP)Si(CH3)2 undergoes electrochemistry different from that of (OEP)Si(C6H5)2 and gives (OEP)Si(CH3)ClO4 and (OEP)-Si(ClO4)2 as successive electrooxidation products. An overall oxidation/reduction scheme for (OEP)Si(R)2 is presented and compared to mechanisms for oxidation/reduction of (OEP)Si(R)X and (OEP)SiX2.",

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AU - Kadish, K. M.

AU - Xu, Q. Y.

AU - Barbe, J. M.

AU - Guilard, R.

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N2 - The synthesis, characterization, and electrochemistry of several (OEP)Si(R)2, (OEP)Si(R)X, and (OEP)SiX2 complexes are reported, where OEP is the dianion of octaethylporphyrin, R is C6H5 or CH3, and X = C1O4- or OH- (OEP)Si(C6H5)2 can be converted to (OEP)Si(C6H5)OH in CHCl3 by irradiation with visible light in the absence of oxygen. Each Si(IV) complex undergoesa reversible electroreduction at theporphyrin ring system. In contrast,the initial electrooxidations of these complexes are irreversible and theoverall processes involve one or more coupled chemical reactions following electron transfer. (OEP)Si-(C6H5)2 can be converted to (OEP)Si(C6H5)OH after oxidation by one electron while further oxidation generates (OEP)Si-(C6H5)ClO4. The latter compound can also be formed by reaction of (OEP)Si(C6H5)2 with 2 equiv of HClO4 in Ph CN.(OEP)Si(CH3)2 undergoes electrochemistry different from that of (OEP)Si(C6H5)2 and gives (OEP)Si(CH3)ClO4 and (OEP)-Si(ClO4)2 as successive electrooxidation products. An overall oxidation/reduction scheme for (OEP)Si(R)2 is presented and compared to mechanisms for oxidation/reduction of (OEP)Si(R)X and (OEP)SiX2.

AB - The synthesis, characterization, and electrochemistry of several (OEP)Si(R)2, (OEP)Si(R)X, and (OEP)SiX2 complexes are reported, where OEP is the dianion of octaethylporphyrin, R is C6H5 or CH3, and X = C1O4- or OH- (OEP)Si(C6H5)2 can be converted to (OEP)Si(C6H5)OH in CHCl3 by irradiation with visible light in the absence of oxygen. Each Si(IV) complex undergoesa reversible electroreduction at theporphyrin ring system. In contrast,the initial electrooxidations of these complexes are irreversible and theoverall processes involve one or more coupled chemical reactions following electron transfer. (OEP)Si-(C6H5)2 can be converted to (OEP)Si(C6H5)OH after oxidation by one electron while further oxidation generates (OEP)Si-(C6H5)ClO4. The latter compound can also be formed by reaction of (OEP)Si(C6H5)2 with 2 equiv of HClO4 in Ph CN.(OEP)Si(CH3)2 undergoes electrochemistry different from that of (OEP)Si(C6H5)2 and gives (OEP)Si(CH3)ClO4 and (OEP)-Si(ClO4)2 as successive electrooxidation products. An overall oxidation/reduction scheme for (OEP)Si(R)2 is presented and compared to mechanisms for oxidation/reduction of (OEP)Si(R)X and (OEP)SiX2.

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Synthesis and Reactivity of σ-Bonded Silicon Metalloporphyrins. Spectroscopic Characterization and Electrochemistry of (P)Si(R)₂, (P)Si(R)X, and (P)SiX₂, Where R = C₆H₅ or CH₃ and X = OH^- or ClO₄^-

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