caa a22 4500 46325368X CHVBK 20180405153348.0 cr unu---uuuuu 170326e20071001xx s 000 0 eng 10.1007/s10562-007-9172-z doi (NATIONALLICENCE)springer-10.1007/s10562-007-9172-z Peroxyacetic Acid Oxidation of Olefins and Alkanes Catalyzed by a Dinuclear Manganese(IV) Complex with 1,4,7-trimethyl-1,4,7-triazacyclononane [Elektronische Daten] [Dalmo Mandelli, Yuriy Kozlov, Camilla Golfeto, Georgiy Shul'pin] Natural terpenes, (−)-limonene and (+)-carvone, can be epoxidized by peroxyacetic acid (PAA) at room temperature if a dinuclear manganese(IV) complex with 1,4,7-trimethyl-1,4,7-triazacyclononane (L), [Mn2L2O3] [PF6]2, is used as a catalyst. The total yield of the epoxides based on the consumed olefins are 97 and 95%, respectively. A kinetic study of the dec-1-ene and cyclohexane oxygenations including the investigation of their simultaneous competitive oxidation was carried out. The olefin epoxidation rate does not depend on dec-1-ene concentration and the dec-1-ene concentration does not affect the rate of cyclohexane oxidation. The cyclohexane oxidation rate is proportional to the alkane concentration. The kinetic analysis led to the conclusion that two species X 1 and X 2 are generated in the system, and there is no their mutual interconversion. The rate equation for the dec-1-ene epoxidation was proposed: W=k +1[cat][PAA], where cat is the initial manganese complex or its derivative, and the constant was determined: k +1=3.5 mol−1dm3s−1. Species X 1 is apparently an effectively epoxidizing manganese peroxo derivative whereas species X 2 is an alkane hydroxylating manganese oxo complex. Springer Science+Business Media, LLC, 2007 Alkanes nationallicence Alkyl hydroperoxides nationallicence Carvone nationallicence Epoxidation nationallicence Homogeneous catalysis nationallicence Limonene nationallicence Manganese complexes nationallicence Olefins nationallicence Oxidation nationallicence Peroxyacetic acid nationallicence Terpenes nationallicence Mandelli Dalmo Faculdade de Química, Pontifícia Universidade Católica de Campinas, Campus I, Rod. D. Pedro I, km 136, Pq. das Universidades, 13086-900, Campinas, SP, Brazil aut Kozlov Yuriy Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina 4, 119991, Moscow, Russia aut Golfeto Camilla Faculdade de Química, Pontifícia Universidade Católica de Campinas, Campus I, Rod. D. Pedro I, km 136, Pq. das Universidades, 13086-900, Campinas, SP, Brazil aut Shul'pin Georgiy Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina 4, 119991, Moscow, Russia aut Catalysis Letters Springer US; http://www.springer-ny.com 118/1-2(2007-10-01), 22-29 1011-372X 118:1-2<22 2007 118 10562 https://doi.org/10.1007/s10562-007-9172-z text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10562-007-9172-z text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Mandelli Dalmo Faculdade de Química, Pontifícia Universidade Católica de Campinas, Campus I, Rod. D. Pedro I, km 136, Pq. das Universidades, 13086-900, Campinas, SP, Brazil aut NATIONALLICENCE 700 1- Kozlov Yuriy Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina 4, 119991, Moscow, Russia aut NATIONALLICENCE 700 1- Golfeto Camilla Faculdade de Química, Pontifícia Universidade Católica de Campinas, Campus I, Rod. D. Pedro I, km 136, Pq. das Universidades, 13086-900, Campinas, SP, Brazil aut NATIONALLICENCE 700 1- Shul'pin Georgiy Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina 4, 119991, Moscow, Russia aut NATIONALLICENCE 773 0- Catalysis Letters Springer US; http://www.springer-ny.com 118/1-2(2007-10-01), 22-29 1011-372X 118:1-2<22 2007 118 10562 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer