An electron-transfer induced migratory insertion reaction originating from a 19-electron cobaltacyclic anion
Identifieur interne : 002150 ( Istex/Curation ); précédent : 002149; suivant : 002151An electron-transfer induced migratory insertion reaction originating from a 19-electron cobaltacyclic anion
Auteurs : Andre Morneau [États-Unis] ; Bernadette T. Donovan-Merkert [États-Unis] ; William E. Geiger [États-Unis]Source :
- Inorganica Chimica Acta [ 0020-1693 ] ; 1999.
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Abstract
The cyclopentadienyl cobaltafluorenyl carbonyl complex Cp(CO)CoC12H8 (3) is reduced in THF in a one-electron irreversible process. The reduction products include the fluorenone radical anion, Fl−, which is proposed to arise through migratory insertion of the CO ligand into the metallacyclic CoC bond of the 19-electron complex 3−. Electrochemical and IR analyses show that bulk electrolysis under N2 gives 1/3 equiv. each of Fl− and CpCo(CO)2 and 2/3 equiv. of a 17-electron anion [CpCoC12H8]− (2−) Under CO the yield of Fl− is quantitative. The insertion product is also formed when the reduction of the analogous phosphine complex Cp(PPh3)CoC12H8 is performed under CO. An equilibrium between 17- and 19-electron compounds is postulated to account for the synthetic and voltammetric observations. When the cobaltacycle Cp(PPh3)CoC4Ph4 (5) is reduced under carbon monoxide, the CO-insertion product is the π-cyclopentadienone complex CpCo(η4-C4Ph4O) (8).
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DOI: 10.1016/S0020-1693(99)00533-2
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Geiger</name><affiliation wicri:level="1"><mods:affiliation>Department of Chemistry, University of Vermont, Burlington, VT 05405, USA</mods:affiliation><country xml:lang="fr">États-Unis</country><wicri:regionArea>Department of Chemistry, University of Vermont, Burlington, VT 05405</wicri:regionArea></affiliation></author></analytic><monogr></monogr><series><title level="j">Inorganica Chimica Acta</title><title level="j" type="abbrev">ICA</title><idno type="ISSN">0020-1693</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1999">1999</date><biblScope unit="volume">300–302</biblScope><biblScope unit="supplement">C</biblScope><biblScope unit="page" from="96">96</biblScope><biblScope unit="page" to="101">101</biblScope></imprint><idno type="ISSN">0020-1693</idno></series><idno type="istex">18D3D4F7433F6FF24BA9BC4886FF768554CF0534</idno><idno type="DOI">10.1016/S0020-1693(99)00533-2</idno><idno type="PII">S0020-1693(99)00533-2</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0020-1693</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Cobalt complexes</term><term>Cyclopentadienyl complexes</term><term>Electron transfer</term><term>Fluorenyl complexes</term><term>Migratory insertion</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The cyclopentadienyl cobaltafluorenyl carbonyl complex Cp(CO)CoC12H8 (3) is reduced in THF in a one-electron irreversible process. The reduction products include the fluorenone radical anion, Fl−, which is proposed to arise through migratory insertion of the CO ligand into the metallacyclic CoC bond of the 19-electron complex 3−. Electrochemical and IR analyses show that bulk electrolysis under N2 gives 1/3 equiv. each of Fl− and CpCo(CO)2 and 2/3 equiv. of a 17-electron anion [CpCoC12H8]− (2−) Under CO the yield of Fl− is quantitative. The insertion product is also formed when the reduction of the analogous phosphine complex Cp(PPh3)CoC12H8 is performed under CO. An equilibrium between 17- and 19-electron compounds is postulated to account for the synthetic and voltammetric observations. When the cobaltacycle Cp(PPh3)CoC4Ph4 (5) is reduced under carbon monoxide, the CO-insertion product is the π-cyclopentadienone complex CpCo(η4-C4Ph4O) (8).</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
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