Doctoral Dissertations

Abstract

"The interaction of diazomalonic esters with olefins in the presence of homogeneous Cu(II) catalyst species has been examined relating to olefin structure effects and catalyst structure effects using partial rate data as a method of determining the mechanistic aspects of the various reactions.

It has been possible to examine the mechanistic details of cyclopropanation, C-H insertion, and both "dimer" forming reactions.

Cyclopropanation proceeds via a transition state including olefin, copper (II), ligands, and carbene C-H insertion results from hydrogen abstraction prior to collapse of the transition state. "Dimer" is formed by the attack of diazo compound on the carbenoid carbon, with subsequent trans elimination of nitrogen and catalyst.

The first copper catalyzed decomposition of a Δ-1 pyrazoline has been observed"--Abstract, page iii.

Advisor(s)

Wulfman, David S., 1934-2013

Committee Member(s)

Poling, Bruce E.
Nicholson, Larry M.
Stoffer, James O.
Hanna, Samir B.

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Publisher

University of Missouri--Rolla

Publication Date

1974

Pagination

ix, 64 pages

Note about bibliography

Includes bibliographical references (pages 59-63).

Rights

© 1974 Robert Stephen McDaniel, Jr., All rights reserved.

Document Type

Dissertation - Open Access

File Type

text

Language

English

Subject Headings

Copper catalystsDecomposition (Chemistry) -- Mathematical modelsMetal complexes

Thesis Number

T 3011

Print OCLC #

6012024

Electronic OCLC #

913832247

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