Doctoral Dissertations

Abstract

"The interaction of diazomalonic esters with olefins in the presence of homogeneous copper(I) and copper(II) catalyst has been examined as a function of olefin structure, solvent media, ionic strength, catalyst structure and catalyst concentration, using partial rate data. It has been possible to determine the fine mechanistic details of the cycloproponation, C-H insertion and "dimer" forming reactions. The initial step is displacement of a ligand from copper by diazo compound in a pre-equilibrium, loss of nitrogen in the rate determining step, return of the ligand, displacement of metal from the carbenoid by olefin, followed by collapse to products. Studies revealed the intimate involvement of catalyst with olefin as well as carbene"--Abstract, page ii.

Advisor(s)

Wulfman, David S., 1934-2013

Committee Member(s)

Nicholson, Larry M.
Webb, William H.
Stoffer, James O.
Gutsche, C. David (Carl David), 1921-
Russell, Robert R.

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Publisher

University of Missouri--Rolla

Publication Date

1971

Journal article titles appearing in thesis/dissertation

  • Preparation and Reactions of Diazomalonic Esters
  • Decomposition of Diazo Compounds by Soluble Metal Complexes

Pagination

xiii, 189 pages

Note about bibliography

Includes bibliographical references.

Rights

© 1971 Billy Wayne Peace, All rights reserved.

Document Type

Dissertation - Open Access

File Type

text

Language

English

Subject Headings

Copper catalysts
Decomposition (Chemistry) -- Mathematical models
Metal complexes

Thesis Number

T 2622

Print OCLC #

6038744

Electronic OCLC #

876712165

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Chemistry Commons

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