FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W3022018596> ?p ?o ?g. }

• W3022018596 endingPage "119" @default.
• W3022018596 startingPage "103" @default.
• W3022018596 abstract "Dinuclear manganese(IV) complex [LMn(O)3MnL](PF6)2 (1, L = 1,4,7-trimethyl-1,4,7-triazacyclononane) efficiently catalyzes epoxidation of sterically accessible olefins, including natural compounds by hydrogen peroxide in acetonitrile at room temperature if a small amount of a carboxylic acid is present in the solution. The kinetics of dec-1-ene epoxidation and accompanying dioxygen evolution (catalase activity) under the action of this system in the presence of acetic acid has been studied. The initial rates of both epoxidation and O2 evolution are proportional to the catalyst initial concentration. First order has been found for catalyst 1 for both processes, whereas the rate dependences of the dec-1-ene epoxidation is first order and the O2 evolution is second order for H2O2. The epoxidation rate increases and the O2 evolution rate decreases with growing of acetic acid concentration. Zero order has been found for dec-1-ene in its epoxidation. The reaction proceeds with an induction period for a few minutes during which changes in the electronic spectra of the reaction solution are observed. It has been proposed that the processes of the alkane oxidation and dioxygen evolution on the one hand and of the olefin epoxidation on the other hand are induced by different intermediate species. An assumption has been made that the epoxidation occurs with participation of oxo-hydroxy Mn(V) derivative [LMnV(O)(O)2(HO)MnIVL]2+, whereas di(hydroperoxy) complex [LMnIII(OOH)(O)2(HOO)MnIVL]+ is responsible for the alkane oxidation with simultaneous dioxygen evolution. The following equations for the initial rates were proposed for [CH3CO2H] = 0.25 mol dm−3: d[epoxide]/dt = keff(epoxide)[1][H2O2] with keff(epoxide) = 2.8–3.7 mol−1 dm3 s−1; d[CyOOH]/dt = keff(CyOOH)[1][H2O2]2[CyH] with keff(CyOOH) = 4.1–6.2 mol−3 dm9 s−1; d[O2]/dt = keff(O2)[1][H2O2]2 with keff(O2) = 2.8–7.0 mol−2 dm6 s−1. Many different carboxylic acids were checked as cocatalysts and it has been found that oxalic acid acts with the highest efficiency in the epoxidation whereas the accompanying catalase activity of the system is very low in this case. It has been also demonstrated that complex 1 is unique catalyst because similar compounds containing only one Mn(IV) center (2) or dinuclear complex with bridging phenylboronic acid (3) are very poor catalysts in the olefin epoxidation. No epoxidation has been found when hydrogen peroxide was replaced by tert-butyl hydroperoxide. The system based on 1, H2O2 and acetic and/or oxalic acid was employed for the efficient epoxidation of terpenes limonene, citral, carvone and linalool, while other terpenes containing sterically hindered double bonds (citronellal, α- and β-isomers of pinene) were epoxidized only with <15% yield. Using limonene as example, it has been demonstrated that regioselectivity of the epoxidation (predominant formation of product with addition of the O atom either to internal ring or external double bond) can be controlled by replacing acetic acid by oxalic acid." @default.
• W3022018596 created "2020-05-13" @default.
• W3022018596 creator A5016099046 @default.
• W3022018596 creator A5026356242 @default.
• W3022018596 creator A5032332220 @default.
• W3022018596 creator A5062839673 @default.
• W3022018596 creator A5065534179 @default.
• W3022018596 creator A5081686788 @default.
• W3022018596 date "2004-11-01" @default.
• W3022018596 modified "2023-10-16" @default.
• W3022018596 title "Oxidations by the system “hydrogen peroxide–dinuclear manganese(IV) complex–carboxylic acid”" @default.
• W3022018596 cites W14481602 @default.
• W3022018596 cites W1558904624 @default.
• W3022018596 cites W1850120019 @default.
• W3022018596 cites W193086721 @default.
• W3022018596 cites W1966968102 @default.
• W3022018596 cites W1966978533 @default.
• W3022018596 cites W1967512934 @default.
• W3022018596 cites W1971378346 @default.
• W3022018596 cites W1972225847 @default.
• W3022018596 cites W1973272263 @default.
• W3022018596 cites W1975200940 @default.
• W3022018596 cites W1978178074 @default.
• W3022018596 cites W1978458801 @default.
• W3022018596 cites W1978484522 @default.
• W3022018596 cites W1979259874 @default.
• W3022018596 cites W1984133498 @default.
• W3022018596 cites W1985071182 @default.
• W3022018596 cites W1986130511 @default.
• W3022018596 cites W1987701604 @default.
• W3022018596 cites W1987711967 @default.
• W3022018596 cites W1988558925 @default.
• W3022018596 cites W1990987978 @default.
• W3022018596 cites W1995144376 @default.
• W3022018596 cites W1996461792 @default.
• W3022018596 cites W1998808813 @default.
• W3022018596 cites W1998872493 @default.
• W3022018596 cites W1998918374 @default.
• W3022018596 cites W2001089160 @default.
• W3022018596 cites W2005998814 @default.
• W3022018596 cites W2006477237 @default.
• W3022018596 cites W2010705033 @default.
• W3022018596 cites W2011412061 @default.
• W3022018596 cites W2013276272 @default.
• W3022018596 cites W2015239581 @default.
• W3022018596 cites W2015864415 @default.
• W3022018596 cites W2016651664 @default.
• W3022018596 cites W2018596155 @default.
• W3022018596 cites W2019233282 @default.
• W3022018596 cites W2019952297 @default.
• W3022018596 cites W2020457705 @default.
• W3022018596 cites W2022819987 @default.
• W3022018596 cites W2023592219 @default.
• W3022018596 cites W2024447680 @default.
• W3022018596 cites W2026343010 @default.
• W3022018596 cites W2031883318 @default.
• W3022018596 cites W2032291118 @default.
• W3022018596 cites W2034981651 @default.
• W3022018596 cites W2037296621 @default.
• W3022018596 cites W2037824336 @default.
• W3022018596 cites W2038587825 @default.
• W3022018596 cites W2040299058 @default.
• W3022018596 cites W2041433990 @default.
• W3022018596 cites W2041476922 @default.
• W3022018596 cites W2043625040 @default.
• W3022018596 cites W2045942910 @default.
• W3022018596 cites W2055210591 @default.
• W3022018596 cites W2057312993 @default.
• W3022018596 cites W2059019886 @default.
• W3022018596 cites W2060073060 @default.
• W3022018596 cites W2060854215 @default.
• W3022018596 cites W2060984881 @default.
• W3022018596 cites W2061864005 @default.
• W3022018596 cites W2063217797 @default.
• W3022018596 cites W2063781162 @default.
• W3022018596 cites W2063954840 @default.
• W3022018596 cites W2068996255 @default.
• W3022018596 cites W2069073216 @default.
• W3022018596 cites W2070357875 @default.
• W3022018596 cites W2070750962 @default.
• W3022018596 cites W2074372933 @default.
• W3022018596 cites W2074533347 @default.
• W3022018596 cites W2075261694 @default.
• W3022018596 cites W2076438625 @default.
• W3022018596 cites W2079160379 @default.
• W3022018596 cites W2083889957 @default.
• W3022018596 cites W2084052917 @default.
• W3022018596 cites W2085791627 @default.
• W3022018596 cites W2086280027 @default.
• W3022018596 cites W2086650273 @default.
• W3022018596 cites W2088004884 @default.
• W3022018596 cites W2089658917 @default.
• W3022018596 cites W2089701417 @default.
• W3022018596 cites W2090524185 @default.
• W3022018596 cites W2091517619 @default.
• W3022018596 cites W2095140339 @default.
• W3022018596 cites W2103789879 @default.
• W3022018596 cites W2106185500 @default.

• next