Late transition metal complexes of a new class of amino-phenylphosphinite pincer ligands bearing crown ether groups have been prepared. The large number of proximal donors allows access to a variety of binding modes, from tridentate to pentadentate coordination. Interconversion between binding modes is modulated by the presence of alkali metal cations capable of interacting with the crown ether group. Mechanistic studies of ligand binding dynamics of Ni and Ir complexes in the presence of cationic additives will be discussed. Hydrogen activation, observed by H/D exchange reactions, is gated by the pincer-crown-ether ligand, proceeding very slowly; in the presence of alkali metal cations, however, dramatic acceleration in the rate of H/D exchange is observed. Catalytic reactions carried out by these systems will also be discussed.

Variable coordination modes and cation-modulated reactivity of pincer-crown-ether complexes

248th National Meeting (2014)

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