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Kinetics and mechanistic studies of molybdenum(2) oxygen(3) (diethyl dtc)(2) (THF)(2) iodine(2)

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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
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.
Subject(s): Enzyme kinetics
Molybdenum enzymes
Chemical kinetics
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/
Owner Institution: FAU
Is Part of Series: Florida Atlantic University Digital Library Collections.