Water-soluble NNN-pincer complexes of cobalt, nickel and palladium: Solid-state structures and catalytic activity
2017
Abstract Neutral NNN-pincer ligand 1 based on a pyridyl core and cyclic amidine pendant arms was synthesized via a straightforward condensation reaction. Its square-planar palladium acetate complex 2 was prepared in methanol and featured a cyclic, hexameric solid-state structure assembled through moderately strong N⋯H⋯O hydrogen bonds involving the ligand backbone and the non-coordinated acetate group. The octahedral, diamagnetic Co(III) complex 3 was prepared via in-situ air oxidation of its Co(II) analog. Its solid-state structure confirmed the oxidation state of the metal and revealed the presence of weak bridging and terminal N H⋯Cl hydrogen bonds. Paramagnetic nickel complex 4 was prepared in a similar fashion to 1 and was postulated to have a covalent attachment of the acetate moieties to the metal. Derivatives 2 and 3 had excellent water solubility and stability while 4 was sparingly soluble in water. Cyclic voltammetry revealed electrochemically reversible electron transfer steps corresponding to the Co(II)/Co(III) and Ni(II)/Ni(III) redox couples at −0.31 V and 1.04 V versus SHE, respectively. Complex 4 displayed catalytic competency towards the thiolation of iodobenzene with dimethyldisulfide and zinc in DMF. In water, 4 was able to catalyze the Negishi cross-coupling of iodobenzene.
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