Kinetics of Oxygen Transfer Reactions Involving Molybdenum Dithiolene Complexes
(1997) In Journal of the Chemical Society, Dalton Transactions p.3997-4004- Abstract
- Oxo transfer reactions from [MoO2(mnt)2]2– [mnt2– = 2,3-disulfanylmaleonitrile dianion (1,2-dicyanoethylenedithiolate)] to the abiological oxygen acceptors PPh3–xEtx (x = 0–3) have been studied spectrophotometrically in acetonitrile. The pseudo-first-order rate constants depend linearly on the concentration of the oxo acceptors. The sequence of reactivity is PEt3 > PEt2Ph > PEtPh2 > PPh3, reflecting the basicities of the phosphines, while the steric influence of the substituents on the phosphorus atom appears to be of minor importance. The activation entropies for the reaction with PEt3 and PPh3 are negative. These observations are in agreement with the proposal that in the intermediate the entering phosphine binds to the... (More)
- Oxo transfer reactions from [MoO2(mnt)2]2– [mnt2– = 2,3-disulfanylmaleonitrile dianion (1,2-dicyanoethylenedithiolate)] to the abiological oxygen acceptors PPh3–xEtx (x = 0–3) have been studied spectrophotometrically in acetonitrile. The pseudo-first-order rate constants depend linearly on the concentration of the oxo acceptors. The sequence of reactivity is PEt3 > PEt2Ph > PEtPh2 > PPh3, reflecting the basicities of the phosphines, while the steric influence of the substituents on the phosphorus atom appears to be of minor importance. The activation entropies for the reaction with PEt3 and PPh3 are negative. These observations are in agreement with the proposal that in the intermediate the entering phosphine binds to the molybdenum complex through the oxygen ligand. Oxidation of HSO3– by [MoO2(mnt)2]2– has also been studied in acetonitrile and in acetonitrile–water mixtures. The reaction exhibits Michaelis–Menten behaviour. In CH3CN–H2O, the rate of the reaction increases as the water concentration decreases; the reacting species appears to be a product from the reaction of the molybdenum starting complex with water. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/960966
- author
- Lorber, Christian ; Plutino, Rosaria ; Elding, Lars Ivar LU and Nordlander, Ebbe LU
- organization
- publishing date
- 1997
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Molybdenum complexes, Oxygen atom transfer, Michaelis–Menten reaction, Activation entropy
- in
- Journal of the Chemical Society, Dalton Transactions
- issue
- 21
- pages
- 3997 - 4004
- publisher
- Royal Society of Chemistry
- external identifiers
-
- scopus:0006084236
- ISSN
- 0300-9246
- DOI
- 10.1039/a704332e
- language
- English
- LU publication?
- yes
- id
- 9410c910-0a36-4e1b-902a-1258c9508d43 (old id 960966)
- date added to LUP
- 2016-04-01 16:10:11
- date last changed
- 2022-01-28 17:49:56
@article{9410c910-0a36-4e1b-902a-1258c9508d43, abstract = {{Oxo transfer reactions from [MoO2(mnt)2]2– [mnt2– = 2,3-disulfanylmaleonitrile dianion (1,2-dicyanoethylenedithiolate)] to the abiological oxygen acceptors PPh3–xEtx (x = 0–3) have been studied spectrophotometrically in acetonitrile. The pseudo-first-order rate constants depend linearly on the concentration of the oxo acceptors. The sequence of reactivity is PEt3 > PEt2Ph > PEtPh2 > PPh3, reflecting the basicities of the phosphines, while the steric influence of the substituents on the phosphorus atom appears to be of minor importance. The activation entropies for the reaction with PEt3 and PPh3 are negative. These observations are in agreement with the proposal that in the intermediate the entering phosphine binds to the molybdenum complex through the oxygen ligand. Oxidation of HSO3– by [MoO2(mnt)2]2– has also been studied in acetonitrile and in acetonitrile–water mixtures. The reaction exhibits Michaelis–Menten behaviour. In CH3CN–H2O, the rate of the reaction increases as the water concentration decreases; the reacting species appears to be a product from the reaction of the molybdenum starting complex with water.}}, author = {{Lorber, Christian and Plutino, Rosaria and Elding, Lars Ivar and Nordlander, Ebbe}}, issn = {{0300-9246}}, keywords = {{Molybdenum complexes; Oxygen atom transfer; Michaelis–Menten reaction; Activation entropy}}, language = {{eng}}, number = {{21}}, pages = {{3997--4004}}, publisher = {{Royal Society of Chemistry}}, series = {{Journal of the Chemical Society, Dalton Transactions}}, title = {{Kinetics of Oxygen Transfer Reactions Involving Molybdenum Dithiolene Complexes}}, url = {{http://dx.doi.org/10.1039/a704332e}}, doi = {{10.1039/a704332e}}, year = {{1997}}, }