cis-Dihydroxylation and epoxidation of alkenes by [Mn(2)O(RCO(2))(2)(tmtacn)(2)]: tailoring the selectivity of a highly H(2)O(2)-efficient catalyst.

de Boer, Johannes W; Brinksma, Jelle; Browne, Wesley R; Meetsma, Auke; Alsters, Paul L; Hage, Ronald; Feringa, Ben L

de Boer, Johannes W; Brinksma, Jelle; Browne, Wesley R; Meetsma, Auke; Alsters, Paul L; Hage, Ronald; Feringa, Ben L.

Afiliación

de Boer JW; Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.

J Am Chem Soc ; 127(22): 7990-1, 2005 Jun 08.

Article en En | MEDLINE | ID: mdl-15926804

RESUMEN

The carboxylic acid promoted cis-dihydroxylation and epoxidation of alkenes catalyzed by [MnIV2O3(tmtacn)2]2+ 1 employing H2O2 as oxidant is described. The use of carboxylic acids at cocatalytic levels not only is effective in suppressing the inherent catalase activity of 1, but also enables the tuning of the catalyst's selectivity. Spectroscopic studies and X-ray analysis confirm that the control arises from the in situ formation of carboxylate-bridged dinuclear complexes, for example, 2 {[MnIII2O(CCl3CO2)2(tmtacn)2]2+} and 3 {[MnII2(OH)(CCl3CO2)2(tmtacn)2]+}, during catalysis. For the first time, the possibility to tune, through the carboxylate ligands employed, both the selectivity and activity of dinuclear Mn-based catalysts is demonstrated. To our knowledge, the system 1/2,6-dichlorobenzoic acid (up to 2000 turnover numbers for cis-cyclooctanediol) is the most active Os-free cis-dihydroxylation catalyst reported to date.

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Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Am Chem Soc Año: 2005 Tipo del documento: Article País de afiliación: Países Bajos Pais de publicación: Estados Unidos

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