Utilize este identificador para referenciar este registo: http://hdl.handle.net/10400.21/2887
Título: Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation
Autor: Milunovic, Miljan N. M.
Martins, Luísa Margarida D. R. S.
Alegria, Elisabete C. B. A.
Pombeiro, Armando J. L.
Krachler, Regina
Trettenhahn, Guenter
Turta, Constantin
Shova, Sergiu
Arion, Vladimir B.
Palavras-chave: Single-pot hydrocarboxylation
Mild peroxidative oxidation
Nonheme iron catalysts
Copper triethnolamine complexes
Alkane hydroxylation
Highly efficient
Data: 2013
Editora: Royal Soc Chemistry
Citação: MILUNOVIC, Miljan N. M.; MARTINS, Luisa M. D. R. S.; ALEGRIA, Elisabete C. B. A. ; POMBEIRO, Armando J. L.; KRACHLER, Regina; TRETTENHAHN, Guenter; TURTA, Constantin; SHOVA, Sergiu; ARION, Vladimir B. - Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation. Dalton Transactions. ISSN 1477-9226. Vol. 42, nr. 40 (2013), p. 14388-14401.
Resumo: Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.
Peer review: yes
URI: http://hdl.handle.net/10400.21/2887
ISSN: 1477-9226
Aparece nas colecções:ISEL - Eng. Quim. Biol. - Artigos

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