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Electron Transfer Chemistry of Organometallic Porphyrins

Electron Transfer Chemistry of Organometallic Porphyrins
有机金属卟啉的电子转移化学
批准号:
08044083
负责人:
FUKUZUMI Shunichi
金额:
$4.48万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for international Scientific Research
财政年份:
1996
资助国家:
日本
项目状态:
已结题
起止时间:
1996 至 1997

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中文摘要
翻译
烷基和芳基金属σ-键合的卟啉的单电子氧化之后通常是σ-键合的有机配体的金属到氮的迁移。本<III><IV>研究结合电化学、紫外-可见光谱、ESR和停流动力学研究了(P)M(R)和(P)M(R)(L)型单氧化有机卟啉的反应和性质,其中P =取代卟啉的二价阴离子:TPP或OEP,M = Co或Fe,R = n-Bu、Et、Me或Ph,L =乙腈或取代的吡啶。我们的研究结果清楚地表明,(TPP)Co^<IV>(R)配合物可以在特定的溶液条件下生成,钴-碳键的断裂通过从R到Co的速率决定性的分子内电子转移发生,这导致R基团的金属到氮的迁移。以类似的方式,芳基σ键合的铁卟啉(OEP)Fe^(R)的单电子氧化<III>导致Fe^中心的形成<IV>,其总是在迁移之前产生。
英文摘要
The one-electron oxidation of alkyl and aryl metal sigma-bonded porphyrins is often followed by a metal to nitrogen migration of the sigma-bonded organic ligand. Several studies of oxidized cobalt sigma-bonded porphyrins have suggested that a Co^<III> pi cation radical rather than a Co^<IV> cation is generated prior to the migration.The present study combines the use of electrochemistry, UV-vis and ESR spectroscopy and stopped flow kinetics to investigate the reactions and properties of singly oxidized organoporphyrins of the type (P) M (R) and (P) M (R)(L) where P = the dianion of substituted porphyrins : TPP or OEP,M = Co or Fe, R = n-Bu, Et, Me or Ph, L = acetonitrile or a substituted pyridine. The results of our studies show clearly that a (TPP) Co^<IV> (R) complex can be generated under specific solution conditions and the cleavage of the cobalt-carbon bond occurs via a rate-determining intramolecular electron transfer from R to Co and this results in a metal to nitrogen migration of the R group. In a similar mannar, one-electron oxidation of an aryl sigma-bonded iron porphyrin, (OEP) Fe^<III> (R) results in the formation of an Fe^<IV> center which is invariably generated prior to migration.
期刊论文(11)
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会议论文
Shunichi Fukuzumi et al.: "Kinetic and Thermodynamic Studies of Iron (III) and Iron (IV) Sigma Bonded Porphyrins.Formation and Reactivity of [(OEP) Fe (R)]^<n+>where OEP is the Dianion of Octaethlporphyrin,n=0,1,2,3and R=C_6H_5,3,4,5-C_6F_3H_2,2,4,6-C_6F_
Shunichi Fukuzumi 等人:“铁 (III) 和铁 (IV) Sigma 键合卟啉的动力学和热力学研究。[(OEP) Fe (R)]^<n > 的形成和反应性,其中 OEP 是八乙基卟啉的二价阴离子,
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Shunichi Fukuzumi et al.: "Kinetic and Thermodynamic Studies of Iron (III) and Iron (IV) Sigma Bonded Porphyrins. Formation and Reactivity of [(OEP)Fe(R)]^<n+> where OEP is the Dianion of Octaethylporphyrin, n = 0, l, 2,3 and R = C_6H_5,3,4,5-C_6F_3H_2,2,
Shunichi Fukuzumi 等人:“铁 (III) 和铁 (IV) Sigma 键合卟啉的动力学和热力学研究。[(OEP)Fe(R)]^<n > 的形成和反应性,其中 OEP 是八乙基卟啉的二价阴离子,
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Shunichi Fukuzumi: "Catalysis on Electron Transfer and the Mechanistic Insight into Redox Reactions" Bull.Chem.Soc.Jpn.70. 1-28 (1997)
Shunichi Fukuzumi:“电子转移催化和氧化还原反应的机理洞察”Bull.Chem.Soc.Jpn.70。
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Shunichi Fukuzumi et al.: "Kinetic and Thermodynamic Studies of Iron(III)and Iron(IV)Sigma Bonded Porphyrins.Formation and Reactivity of [(OEP)Fe(R)]^<n+> where OEP is the Dianion of Octaethylporphyrin,n=0,1,2,3 and R=C_6H_5,3,4,5-C_6F_3H_2,2,4,6-C_6F_3H_
Shunichi Fukuzumi 等人:“铁(III)和铁(IV)Sigma键合卟啉的动力学和热力学研究。[(OEP)Fe(R)]^<n>的形成和反应性,其中OEP是八乙基卟啉的二价阴离子,
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