Synthesis of Tridentate 2,6-Bis(imino)pyridyl Ruthenium(II) Complexes with N-Heterocyclic Carbene Ligands: Activation of Imidazolium Salts

초록

Low-valent Ru(0) complexes, [η2-N3]Ru(η6-Ar) (1) or {[N3]Ru}2(μ-N2) (2), where Ar = C6H6 or C6H5Me, and [N3] = 2,6-(2,4,6-(CH3)3C6H2N -CCH3)2C5H3N, activate C-H bonds in imidazolium salts to produce bis(imino)pyridyl ruthenium-(imidazolidin-2-ylidene) complexes, [N3]Ru(H)(X)(NHC) (4) (X = halides and tosylate). Formation of 4 is most likely to proceed via C-H oxidative addition, followed by anion coordination, which is expected to be a useful pathway in synthesizing new complexes with both N-heterocyclic carbene (NHC) and hydride ligands. A zwitterionic ruthenium complex with an ylidic ligand, bis(imino)pyridyl ruthenium-(2-methyleneimidazoline) complex, 7, was also successfully isolated and fully characterized. The 1H NMR spectra and the solid-state structure confirm that complex 7 is an ylidic transition-metal complex with both NHC and hydride ligands, which was formed through the activation of imidazolium salts. © 2014 American Chemical Society.

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