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Kinetics and mechanistic studies of molybdenum(2) oxygen(3) (diethyl dtc)(2) (THF)(2) iodine(2)
- Date Issued:
- 1992
- Summary:
- A study of the kinetic behavior of the oxygen atom transfer reaction of Mo2o3 (Et2dtc)2 (THF) 2I2, (I), with a variety of derivatives of pyridine N-oxides has been performed. The reaction behaves in pseudo-first-order fashion under conditions of excess N-oxide. Plots of kobs vs. [N-oxide] do not give straight lines, while plots of 1/kobs vs. 1/[N-oxide] are linear. The rate constant k is taken as the inverse of the slope of this latter plot. There is a marked dependence of the rate on the functional group in the 4-position of the pyridine ring with the relative rates -CH3 > -H > -Cl > -CN. The above observations can be used to support a mechanism in which a rapid pre-equilibrium, with a large equilibrium constant, is followed by a rate-determining breaking of the Mo-O-Mo bridge.
Title: | Kinetics and mechanistic studies of molybdenum(2) oxygen(3) (diethyl dtc)(2) (THF)(2) iodine(2). |
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Name(s): |
Abburi, Chakravarthi. Florida Atlantic University, Degree grantor Baird, Donald M., Thesis advisor |
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Type of Resource: | text | |
Genre: | Electronic Thesis Or Dissertation | |
Issuance: | monographic | |
Date Issued: | 1992 | |
Publisher: | Florida Atlantic University | |
Place of Publication: | Boca Raton, Fla. | |
Physical Form: | application/pdf | |
Extent: | 128 p. | |
Language(s): | English | |
Summary: | A study of the kinetic behavior of the oxygen atom transfer reaction of Mo2o3 (Et2dtc)2 (THF) 2I2, (I), with a variety of derivatives of pyridine N-oxides has been performed. The reaction behaves in pseudo-first-order fashion under conditions of excess N-oxide. Plots of kobs vs. [N-oxide] do not give straight lines, while plots of 1/kobs vs. 1/[N-oxide] are linear. The rate constant k is taken as the inverse of the slope of this latter plot. There is a marked dependence of the rate on the functional group in the 4-position of the pyridine ring with the relative rates -CH3 > -H > -Cl > -CN. The above observations can be used to support a mechanism in which a rapid pre-equilibrium, with a large equilibrium constant, is followed by a rate-determining breaking of the Mo-O-Mo bridge. | |
Identifier: | 14828 (digitool), FADT14828 (IID), fau:11616 (fedora) | |
Collection: | FAU Electronic Theses and Dissertations Collection | |
Note(s): |
Charles E. Schmidt College of Science Thesis (M.S.)--Florida Atlantic University, 1992. |
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Subject(s): |
Enzyme kinetics Molybdenum enzymes Chemical kinetics |
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Held by: | Florida Atlantic University Libraries | |
Persistent Link to This Record: | http://purl.flvc.org/fcla/dt/14828 | |
Sublocation: | Digital Library | |
Use and Reproduction: | Copyright © is held by the author, with permission granted to Florida Atlantic University to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder. | |
Use and Reproduction: | http://rightsstatements.org/vocab/InC/1.0/ | |
Host Institution: | FAU | |
Is Part of Series: | Florida Atlantic University Digital Library Collections. |