1997 Fiscal Year Final Research Report Summary
Free Radical Substitution Occurring in Quasi-Aromatic Metal Chelate Rings
| Project/Area Number |
09440247
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
物質変換
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| Research Institution | Sophia University |
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Principal Investigator |
SUGIMORI Akira Sophia University, Department of Chemistry; Professor, 理工学部, 教授 (40053590)
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| Project Period (FY) |
1997 – 1998
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| Keywords | Metalladithiolene / Free radical substitution / Azobis(isobutyronitrile) / Dibenzoyl peroxide / N-Halosuccinimide / Benzoylthio-substitution / Arylthio-substitution |
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| Research Abstract |
We have carried out various reactions, especially, free radical reactions, in quasi-aromatic metal chelate rings (mainly in metalladithiolene rings) to clarify their unique valence states (aromatic and unsaturated character).
The carbon-centered radical derived from 2,2-azobis (isobutyronitrile) undergoes substitution both in cobaltadithiolene rings in [CpCo(SィイD22ィエD2CィイD22ィエD2HX)] and in nickeladithiolene ring in [Ni(SィイD22ィエD2CィイD22ィエD2HX)ィイD22ィエD2]. The sulfur-centered radicals such as benzoylthio and arylthio radicals afford substitution products in the reaction with [CpCo(SィイD22ィエD2CィイD22ィエD2HX)]-type cobaltadithiolenes.
This type of reactions is the first example of radical substitution reaction which occurs in quasi-aromatic metal chelate rings. Our discovery will afford an important opportunity to cultivate a new field for radical chemistry in the border of inorganic and organic chemistry.
The substitution by sulfur-centered radicals occurs in the metal chelate rings in acetylacetonatometal complexes. This shows the generality of the free radical substitution in quasi-aromatic metal chelate rings.
In addition we found that another type ionic substitution occurs in cobaltadithiolene rings in the reactions with dibenzoyl peroxide or with N-halosuccinimides.
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