Experimental and Ab initio kinetic isotope effect studies of reaction mechanisms /
Experimental KIEs for several key reactions have been determined using the simultaneous, natural abundance KIE technique. Ab initio and density functional theory (DFT) calculations have been employed with great success as an aid in interpretation of KIEs. KIEs provide information about the nature of...
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| Format: | Thesis Book |
| Language: | English |
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[Place of publication not identified] :
[publisher not identified] ;
1999.
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| Subjects: | |
| Online Access: | http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=733670711&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD |
| Summary: | Experimental KIEs for several key reactions have been determined using the simultaneous, natural abundance KIE technique. Ab initio and density functional theory (DFT) calculations have been employed with great success as an aid in interpretation of KIEs. KIEs provide information about the nature of the transition state of the rate-limiting step, facilitating the evaluation of possible reaction mechanisms. The Sharpless asymmetric dihydroxylation has been shown to have a (3+2) mechanism, putting to end a long term controversy. The transition state of the ozonolysis reaction has been investigated and been shown to be much earlier than previous predictions. Experimental KIEs for the Sharpless asymmetric elucidation point to a versatile catalyst capable of accommodating substrates with different steric requirements. The transition state for the hydrogenation reaction has been shown to possess significant 3-centered 2-electron character. Literature experimental KIEs for the aromatic Claisen rearrangement have been demonstrated to be inaccurate by new experimental and theoretical KIEs which support a much later transition state than previously thought. The unique aldehydic isotope effect of 1.5 from bacterial luciferase-catalyzed reaction was explained with the aid of ab initio calculations. The diimide reduction of alkenes was investigated with theoretical and experimental KIEs and the effect of tunneling is considered. |
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| Item Description: | Vita. "Major Subject: Chemistry". |
| Physical Description: | xvii, 305 leaves : illustrations ; 28 cm. Issued also on microfiche from University Microfilm Inc. |
| Bibliography: | Includes bibliographical references (leaves 157-168). |