As we broaden our understanding of the role of palladium in cross-coupling reactions, more frequently are odd-oxidation state palladium intermediates being proposed in catalytic cycles. However, due to a lack of isolable mononuclear palladium(I) complexes, our knowledge of the reactivity from this oxidation state is limited. Herein we describe the first example of an isolated, catalytically competent mononuclear palladium(I) complex bearing a macrocyclic pyridinophane ligand which demonstrates activity towards Csp<sup>2</sup>-Csp<sup>3</sup> Kumada cross coupling reactions. Mechanistic investigation suggests that the cross-coupling reaction occurs through a I-III-I catalytic cycle, with evidence of direct oxidative addition of aryl halides occurring directly at the palladium(I) center to generate an organometallic palladium(III) intermediate.

Synthesis, characterization, and catalytic activity of mononuclear palladium (I) complexes

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