UC San Diego

The first chapter of this manuscript describes the preparation of a new family of cyclic (alkyl)(amino) carbenes (CAAC). Utilizing a three step synthetic strategy featuring a key [4+2] cyclization, we build the CAAC ring on a barrelene scaffold, distinguishing these rigid carbenes as cyclic (amino)(barrelene)carbenes (CABC). We show this framework, when used in a metal complex, introduces two barrelene hydrogens that are in close contact with the metal center.The second chapter of this manuscript details a new synthetic procedure for the preparation of CAAC, BiCAAC, and CABC copper (I) chloride complexes from their corresponding iminium salts. Unlike NHCs, whose copper complexes can be directly prepared from their imidazolium salts, CAAC copper complexes are prepared from their free carbenes- that is if this method allows the formation of the monomeric copper complex in lieu of the cationic biscarbene copper complex. We show that these copper complexes can be obtained in one step by refluxing the iminium salts with sodium acetate and copper chloride. The third chapter of this manuscript explores the stabilization of a reactive dichlorosilaimine by steric exclusion. Featuring a highly polarized silicon nitrogen double bond, this silicon species was formerly stabilized by an NHC. Capitalizing on sterically encumbered anilines, we capture a potassium chloride adduct of a dichlorosilaimine and present spectroscopic evidence for a base-free dichlorosilaimine.