Electrophilic Halogenation–Reductive Elimination Chemistry of Organopalladium and -Platinum Complexes

CONSPECTUS: Transition metal-catalyzed organic transformations often reveal competing reaction pathways. Determining the factors that control the selectivity of such reactions is of extreme importance for the design of reliable synthetic protocols. Herein, we present the account of our studies over the past decade aimed at understanding the selectivity of reductive elimination chemistry of organotransition metal complexes under electrophilic halogenation conditions. Much of our effort has focused on finding the conditions for selective formation of carbon (aryl)-halogen bonds in the presence of competing C-C reductive elimination alternatives. In most cases, the latter was the thermodynamically preferred pathway; however, we found that the reactions could be diverted toward the formation of aryl-iodine and aryl-bromine bonds under kinetic conditions. Of particular importance was to maintain the complex geometry that prohibits C-C elimination while allowing for the elimination of carbon-halogen bonds. This was achieved by employing sterically rigid diphosphine ligands which prevented isomerization within a series of Pt(IV) complexes. It was also important to understand that the neutral M(IV) products often observed or isolated in the oxidative addition reactions are not necessarily the intermediates in the reductive elimination chemistry as it generally takes place from unsaturated species formed en route to relatively stable M(IV) complexes. While aryl-halide reductive elimination for heavier halogens can be competitive with aryl-aryl coupling in diaryl M(IV) complexes, the latter reaction always prevails over aryl-fluoride bond formation. Even when one of the aryl groups is a part of a rigid cyclometalated ligand C-C coupling is still the dominant reaction pathway. However, when one of the aryl groups is replaced with a phenolate donor aryl-F bond formation becomes preferred over C-O bond elimination. During our studies, other interesting reactions have been discovered. For example, the fluorination of the C(sp(3))-H bond can be very selective and compete favorably with C-C coupling. Also, in electron-poor complexes, metal oxidation can have higher energy than oxidation of the coordinated iodo ligand resulting in I-F elimination instead of the formation of aryl-I bond. Overall, electrophilic fluorination can lead to often very selective elimination reactions giving new C-C, C-I, C-F, or I-F bonds, with this selectivity dependent on the metal center, supporting ligands, complex geometry, and electrophilic fluorine source. Together with the many reports on the halogenation of organometallic compounds that appeared in recent years, our results contribute to understanding the requirements for selective transformations under electrophilic conditions and design of new synthetic methods for making organohalogen compounds.