Decarboxylative coupling reactions offer an attractive route to generate functionalized arenes from simple and readily available carboxylic acid coupling partners, yet they are underutilized due to limitations in the scope of carboxylic acid coupling partner. Here we report that the field effect parameter (F) has a substantial influence on the rate of decarboxylation of well-defined silver benzoate complexes. This finding provides the opportunity to surpass current substrate limitations associated with decarboxylation and to enable widespread utilization of decarboxylative coupling reactions.

Transition metal-catalyzed decarboxylative coupling reactions have received considerable attention in recent years as a method to obtain biaryl compounds. However, the oxidative version of this reaction class is still in its infancy, limited to specific substitution patterns on the benzoic acidsortho-substitution -used in these transformations. This thesis describes our attempts to understand the key decarboxylation step of this important class of reactions.The first chapter of this thesis discusses an introduction into cross-coupling reactions, decarboxylative cross-coupling reactions, and outlines relevant physical organic parameters. The following chapter details the synthesis of a series of (1,10-phenanthroline)silver(benzoate) complexes. This chapter also describes their usage in the development of a model of the decarboxylation of the (phen)Ag(benzoate) complexes enabling the prediction of new benzoic acids to be used in oxidative decarboxylative coupling reactions. The last chapter discusses our recent progress on the extension of our decarboxylation methodology to silver heteroaromatic acid carboxylates. This final chapter also describes our preliminary attempts to correlate the rates of decarboxylation of Ag(heteroaromatic carboxylate) complexes with various electronic parameters.