Journal
DALTON TRANSACTIONS
Volume 42, Issue 40, Pages 14388-14401Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3dt50966d
Keywords
-
Categories
Funding
- Austrian Science Fund [P19629-N19]
- Fundacao para a Ciencia e a Tecnologia (FCT), Portugal
- European Regional Development Fund, Sectoral Operational Programme 'Increase of Economic Competitiveness', Priority Axis 2 [SOP IEC-A2-O2.1.2-2009-2, ID 570, COD SMIS-CSNR: 12473, 129/2010-POLISILMET]
- [PTDC/QUI-QUI/102150/2008]
- [PTDC/EQU-EQU/122025/2010]
- [PEst-OE/QUI/UI0100/2011]
- Fundação para a Ciência e a Tecnologia [PEst-OE/QUI/UI0100/2011] Funding Source: FCT
- Austrian Science Fund (FWF) [P19629] Funding Source: Austrian Science Fund (FWF)
Ask authors/readers for more resources
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available