from first principles PP-I-1

OY-IV-2Solvent-Free Allylic Oxidation of Alkenes with O 2 Mediated byFe- and Cr-MIL-101Skobelev I.Y. 1 , Sorokin A.B. 2 , Kovalenko K.A. 3 ,Fedin V.P. 3 , Kholdeeva O.A. 11 Boreskov Institute of Catalysis, Novosibirsk, Russia2 Institut de Recherches sur la Catalyse et l’Environnement de Lyon (IRCELYON), CNRS,Villeurbanne, France3 Nikolaev Institute of Inorganic Chemistry, Novosibirsk, Russiaskobelev_igor@mail.ruThe mesoporous chromium and iron terephthalates, Cr- and Fe-MIL-101 have a rigid zeotypecrystal structure, consisting of quasi-spherical cages of two modes (29 and 34 Å) accessiblethrough windows of ca 12 and 16 Å [1, 2]. Both materials possess large surface areas andmesopore volumes (typically, 3200-3900 m 2 /g and 1.4-2.1 cm 3 /g, respectively) as well ashave good solvolytic and thermal stabilities (up to 300 and 180 o C, respectively). Numerouscoordinatively unsaturated transition metal sites can be easily created by a thermal activationin vacuum. All these allow considering Cr- and Fe-MIL-101 as prospective catalyticmaterials. Herein we report on the recent achievements in the catalytic applications of Fe- andCr-MIL-101 in the liquid-phase selective oxidation of alkenes.Both Fe and Cr-MIL-101 were found to catalyse allylic oxidation of alkenes with molecularoxygen in the absence of additional organic solvent [3]. The nature of the active metal had astrong impact on the product distribution. In both cyclohexene and α-pinene oxidation withO 2 , Cr-MIL-101 allowed achieving higher selectivities towards enol/enone products than Fe-MIL-101. Cyclohexene or α-pinene oxidation over Cr-MIL-101 gave 94% cyclohexenol/-onetotal selectivity at 16% cyclohexene conversion or 70% verbenol/-one selectivity at 26% α-pinene conversion, while in the presence of Fe-MIL-101 only 73% selectivity tocyclohexenol/-one or 33% to verbenol (only traces of verbenone were found) at 8-12%substrate conversions were reached. Fe-MIL-101 demonstrated quite different productdistributions depending on the reaction temperature due to the different oxidationmechanisms.[1] Férey G., Mellot-Draznieks C., Serre C., Millange F., Dutour J., Surble S., Margiolaki I., Science,309 (2005) 2040.[2] Bauer S., Serre C., Devic T., Horcajada P., Marrot J., Férey G., Stock N., Inorg. Chem. 47 (2008) 7568.[3] Maksimchuk N.V., Zalomaeva O.V., Skobelev I.Y., Kovalenko K.A., Fedin V.P., Kholdeeva O.A.Proc. R. Soc. A 2012, doi:10.1098/rspa.2012.0072.103