Oxygen-Atom Transfer from Iodosylarene Adducts of a Manganese(IV) Salen Complex: Effect of Arenes and Anions on I(III) of the Coordinated Iodosylarene
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† Institute for Molecular Science and Okazaki Institute for Integrative Bioscience, National Institutes of Natural Sciences, Myodaiji, Okazaki 444-8787, Japan
Department of Functional Molecular Science, The Graduate University for Advanced Studies (SOKENDAI), Myodaiji, Okazaki 444-8787, Japan
§ Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 minami-Osawa, Hachioji, Tokyo 192-0397, Japan
Inorg. Chem., Article ASAP
DOI: 10.1021/ic401270j
Publication Date (Web): August 2, 2013
Copyright © 2013 American Chemical Society
*E-mail: hiro@ims.ac.jp.
Abstract
This paper reports preparation, characterization, and reactivity of iodosylarene adducts of a manganese(IV) salen complex. In order to systematically investigate steric and electronic factors that control reactivity and selectivity, we prepared iodosylarene adducts from iodosylbenzene, iodosylmesitylene, 2,4,6-triethyliodosylbenzene, and pentafluoroiodosylbenzene. We also investigated the effect of anions on I(III) by using chloride, benzoate, and p-toluenesulfonate. Spectroscopic studies using 1H NMR, electron paramagnetic resonance, infrared spectroscopy, and electrospray ionization mass spectrometry show that these iodosylarene adducts are manganese(IV) complexes bearing two iodosylarenes as external axial ligands. Reactions with thioanisole under the pseudo-first-order conditions show that the electron-withdrawing pentafluorophenyl group and thep-toluenesulfonate anion on I(III) significantly accelerate the oxygen-atom transfer. The high reactivity is correlated with a weakened I–OMn bond, as indicated by IR spectroscopy and mass spectrometry. Stoichiometric reactions with styrenes show that both enantioselectivity and diastereoselectivity are dependent on the arenes and anions on I(III) of the coordinate iodosylarenes. Notably, the pentafluorophenyl group and the p-toluenesulfonate anion suppress the cis-to-trans isomerization in the epoxidation of cis-β-methylstyrene. The present results show that iodosylarene adducts of manganese(IV) salen complexes are indeed active oxygen-atom-transfer reagents and that their reactivity and selectivity are regulated by steric and electronic properties of the arenes and anions on I(III) of the coordinated iodosylarenes.
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