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Sabater MJ, Alvaro M, García H, et al. Laser flash photolysis study of Jacobsen catalyst and related manganese(III) salen complexes. Relevance to catalysis. J Am Chem Soc. 2001;123(29):7074-80doi: 10.1021/ja003371o.
Sabater, M. J., Alvaro, M., García, H., Palomares, E., & Scaiano, J. C. (2001). Laser flash photolysis study of Jacobsen catalyst and related manganese(III) salen complexes. Relevance to catalysis. Journal of the American Chemical Society, 123(29), 7074-80. https://doi.org/10.1021/ja003371o
Sabater, M J, et al. "Laser flash photolysis study of Jacobsen catalyst and related manganese(III) salen complexes. Relevance to catalysis." Journal of the American Chemical Society vol. 123,29 (2001): 7074-80. doi: https://doi.org/10.1021/ja003371o
Sabater MJ, Alvaro M, García H, Palomares E, Scaiano JC. Laser flash photolysis study of Jacobsen catalyst and related manganese(III) salen complexes. Relevance to catalysis. J Am Chem Soc. 2001 Jul 25;123(29):7074-80. doi: 10.1021/ja003371o. PMID: 11459486.
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J Am Chem Soc. 2001 Jul 25;123(29):7074-80. doi: 10.1021/ja003371o.

Laser flash photolysis study of Jacobsen catalyst and related manganese(III) salen complexes. Relevance to catalysis.

Journal of the American Chemical Society

M J Sabater, M Alvaro, H García, E Palomares, J C Scaiano

Affiliations

  1. Departamento de Química, Instituto de Tecnología Química UPV-CSIC, Universidad Politécnica de Valencia, Apartado 22012, 46071 Valencia, Spain.

PMID: 11459486 DOI: 10.1021/ja003371o

Abstract

The laser flash photolysis and emission properties of a set of five-coordinate manganese(III) Schiff-base complexes have been examined. In contrast to the intramolecular electron transfer between Mn3+ and the equatorial salen ligand reported to occur in the absence of axial coordination, our laser flash photolysis study has shown that the reactivity of the respective excited states is appreciably influenced by the electron donor strength of the apical ligand at the metal center. In fact, homolytic and heterolytic photocleavage of the metal-ligand apical bond can be the most important processes upon laser excitation, their relative contribution being influenced by medium effects and the sigma-charge donation of the axial ligand. On the other hand, the detection of reactive intermediates such as the oxomanganese(V) salen complex (lambda(max) 530 nm) by laser flash photolysis opens the way to apply this fast detection technique to the study of reaction mechanisms in catalysis by metallic complexes. As a matter of fact, quenching of oxomanganese(V) salen by simple alkenes has been observed by laser flash.

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