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Catalytic Oxidation of Alkanes and Alkenes by H2O2 with a mu-Oxido Diiron(III) Complex as Catalyst/Catalyst Precursor

Das, Biswanath LU ; Al-Hunaiti, Afnan; Haukka, Matti; Demeshko, Serhiy; Meyer, Steffen; Shteinman, Albert A.; Meyer, Franc; Repo, Timo and Nordlander, Ebbe LU (2015) In European Journal of Inorganic Chemistry p.3590-3601
Abstract
A new mu-oxo diiron(III) complex of the lithium salt of the pyridine-based unsymmetrical ligand 3-[(3-{[bis(pyridin-2-ylmethyl)amino]methyl}-2-hydroxy-5-methylbenzyl)(pyridin2-ylmethyl)amino] propanoate (LiDPCPMPP), [Fe-2(mu-O)(LiDPCPMPP)(2)](ClO4)(2), has been synthesized and characterized. The ability of the complex to catalyze oxidation of several alkanes and alkenes has been investigated by using CH3COOH/H2O2 (1:1) as an oxidative system. Moderate activity in cyclohexane oxidation (TOF = 33 h(-1)) and good activity in cyclohexene oxidation (TOF = 72 h(-1)) were detected. Partial retention of configuration (RC = 53%) in cis- and trans-1,2-dimethylcyclohexane oxidation, moderate 3 degrees/2 degrees selectivity (4.1) in adamantane... (More)
A new mu-oxo diiron(III) complex of the lithium salt of the pyridine-based unsymmetrical ligand 3-[(3-{[bis(pyridin-2-ylmethyl)amino]methyl}-2-hydroxy-5-methylbenzyl)(pyridin2-ylmethyl)amino] propanoate (LiDPCPMPP), [Fe-2(mu-O)(LiDPCPMPP)(2)](ClO4)(2), has been synthesized and characterized. The ability of the complex to catalyze oxidation of several alkanes and alkenes has been investigated by using CH3COOH/H2O2 (1:1) as an oxidative system. Moderate activity in cyclohexane oxidation (TOF = 33 h(-1)) and good activity in cyclohexene oxidation (TOF = 72 h(-1)) were detected. Partial retention of configuration (RC = 53%) in cis- and trans-1,2-dimethylcyclohexane oxidation, moderate 3 degrees/2 degrees selectivity (4.1) in adamantane oxidation, and the observation of a relatively high kinetic isotope effect for cyclohexane oxidation (KIE = 3.27) suggest partial metal-based oxidation, probably in tandem with free-radical oxidation. Low-temperature UV/Vis spectroscopy and mass spectrometric studies in the rapid positive detection mode indicate the formation of a transient peroxido species, [Fe-2(O)(O-2)-(LiDPCPMPP)(2)](2+), which might be an intermediate in the metal-based component of the oxidation process. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Monooxygenases, Iron, Lithium, Oxidation, Homogeneous catalysis
in
European Journal of Inorganic Chemistry
issue
21
pages
3590 - 3601
publisher
John Wiley & Sons
external identifiers
  • wos:000359297800024
  • scopus:84938200504
ISSN
1099-0682
DOI
10.1002/ejic.201500576
language
English
LU publication?
yes
id
11c63ac1-e118-4088-92b1-7be28347df1b (old id 7975567)
date added to LUP
2015-09-24 15:14:06
date last changed
2017-10-08 03:08:05
@article{11c63ac1-e118-4088-92b1-7be28347df1b,
  abstract     = {A new mu-oxo diiron(III) complex of the lithium salt of the pyridine-based unsymmetrical ligand 3-[(3-{[bis(pyridin-2-ylmethyl)amino]methyl}-2-hydroxy-5-methylbenzyl)(pyridin2-ylmethyl)amino] propanoate (LiDPCPMPP), [Fe-2(mu-O)(LiDPCPMPP)(2)](ClO4)(2), has been synthesized and characterized. The ability of the complex to catalyze oxidation of several alkanes and alkenes has been investigated by using CH3COOH/H2O2 (1:1) as an oxidative system. Moderate activity in cyclohexane oxidation (TOF = 33 h(-1)) and good activity in cyclohexene oxidation (TOF = 72 h(-1)) were detected. Partial retention of configuration (RC = 53%) in cis- and trans-1,2-dimethylcyclohexane oxidation, moderate 3 degrees/2 degrees selectivity (4.1) in adamantane oxidation, and the observation of a relatively high kinetic isotope effect for cyclohexane oxidation (KIE = 3.27) suggest partial metal-based oxidation, probably in tandem with free-radical oxidation. Low-temperature UV/Vis spectroscopy and mass spectrometric studies in the rapid positive detection mode indicate the formation of a transient peroxido species, [Fe-2(O)(O-2)-(LiDPCPMPP)(2)](2+), which might be an intermediate in the metal-based component of the oxidation process.},
  author       = {Das, Biswanath and Al-Hunaiti, Afnan and Haukka, Matti and Demeshko, Serhiy and Meyer, Steffen and Shteinman, Albert A. and Meyer, Franc and Repo, Timo and Nordlander, Ebbe},
  issn         = {1099-0682},
  keyword      = {Monooxygenases,Iron,Lithium,Oxidation,Homogeneous catalysis},
  language     = {eng},
  number       = {21},
  pages        = {3590--3601},
  publisher    = {John Wiley & Sons},
  series       = {European Journal of Inorganic Chemistry},
  title        = {Catalytic Oxidation of Alkanes and Alkenes by H2O2 with a mu-Oxido Diiron(III) Complex as Catalyst/Catalyst Precursor},
  url          = {http://dx.doi.org/10.1002/ejic.201500576},
  year         = {2015},
}