First-row metal complexes have recently become attractive targets as catalysts for fine chemical synthesis as replacements for their more toxic and less abundant second- and third-row congeners. Limiting the application of these metals to industrial processes is the tendency toward single-electron redox.  Recently, we have discovered a Co(I) phosphine complex that participates in C�N cross-coupling reactions between hexamethyldisilazide and haloarenes that appears to avoid radical chemistry in favor of the two-electron processes that are typically associated with palladium-catalyzed amination reactions. This presentation will discuss kinetic studies that identify an oxidative addition/reductive elimination pathway and the role of the disilazide ligand in enabling two-electron catalysis with Co(I). Various spectroscopic studies will be discussed as well as the methodology toward the cross-coupling of sterically-demanding alpha-branched nucleophiles.

Development and mechanistic investigations of cobalt(I)-mediated aryl amination reactions mediated via two-electron redox

248th National Meeting (2014)

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