Catalytic Oxidation of Alkanes and Alkenes by H2O2 with a mu-Oxido Diiron(III) Complex as Catalyst/Catalyst Precursor
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/7975567
- author
- Das, Biswanath LU ; Al-Hunaiti, Afnan ; Haukka, Matti ; Demeshko, Serhiy ; Meyer, Steffen ; Shteinman, Albert A. ; Meyer, Franc ; Repo, Timo and Nordlander, Ebbe LU
- organization
- publishing date
- 2015
- 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 Inc.
- external identifiers
-
- wos:000359297800024
- scopus:84938200504
- ISSN
- 1099-0682
- DOI
- 10.1002/ejic.201500576
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
- id
- 11c63ac1-e118-4088-92b1-7be28347df1b (old id 7975567)
- date added to LUP
- 2016-04-01 10:14:18
- date last changed
- 2022-04-12 03:24:19
@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}}, keywords = {{Monooxygenases; Iron; Lithium; Oxidation; Homogeneous catalysis}}, language = {{eng}}, number = {{21}}, pages = {{3590--3601}}, publisher = {{John Wiley & Sons Inc.}}, 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}}, doi = {{10.1002/ejic.201500576}}, year = {{2015}}, }