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Metal Salt Catalyzed Carbenoids, Billy W. Peace

Doctoral Dissertations

"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 …