Oxygen-Atom Transfer from Iodosylarene Adducts of a Manganese(IV) Salen Complex: Effect of Arenes and Anions on I(III) of the Coordinated Iodosylarene
详细信息 查看全文
- 作者：Chunlan Wang ; Takuya Kurahashi ; Kensuke Inomata ; Masahiko Hada ; Hiroshi Fujii
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：August 19, 2013
- 年：2013
- 卷：52
- 期：16
- 页码：9557-9566
- 全文大小：519K
- 年卷期：v.52,no.16(August 19, 2013)
- ISSN：1520-510X
文摘
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 the p-toluenesulfonate anion on I(III) significantly accelerate the oxygen-atom transfer. The high reactivity is correlated with a weakened I鈥揙Mn 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-尾-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.