Cooperative Metal–Ligand Assisted E/Z Isomerization and Cyano Activation at CuII and CoII Complexes of Arylhydrazones of Active Methylene Nitriles

New (E/Z)-2-(2-(1-cyano-2-methoxy-2-oxoethylidene)­hydrazinyl)­benzoic acid (H2L4) and known sodium 2-(2-(dicyanomethylene)­hydrazinyl)­benzenesulfonate (NaHL1), 2-(2-(dicyano-methylene)­hydrazinyl)­benzoic acid (H2L2), and sodium (E/Z)-2-(2-(1-cyano-2-methoxy-2-oxoethylidene)­hydrazinyl)­benzenesulfonate (NaHL3) were used in the template synthesis of a series of CuII and CoII complexes [Cu­(H2O)2L1a]·H2O (1), [Cu­(H2O)­(3-pyon)­L1b]·H2O (2), [Cu­(H2O)­(4-pyon)­L1b] (3), [Co­(H2O)­((CH3)2NCHO)­(μ-L2a)]2·(CH3)2NCHO (4), [Cu3(μ3-OH)­(NO3)­(CH3OH)­(μ2-X)3(μ2-HL3)] (5), [Cu­(H2O)­(py)­L3]·H2O (6), [Cu­(H2O)2(μ-L4)]6·6H2O (7), [Cu­(2-cnpyb)2(L1b)2]·2H2O (8), [Cu­(2-cnpya)2(L1a)2]·2H2O (9), and [Cu­(H2O)­(4-cnpy)­(L1a)2] (10), where 3-pyon = 1-(pyridin-3-yl)­ethanone, 4-pyon = 1-(pyridin-4-yl)­ethanone, py = pyridine, HX = syn-2-pyridinealdoxime, 4-cnpy = 4-cyanopyridine; 2-cnpya, 2-cnpyb, L1a, L1b, L2a are the ligands derived from nucleophilic attack of methanol (a) or water (b) on a cyano group of 2-cyanopyridine (2-cnpy), L1 or L2, respectively, giving the corresponding iminoesters (2-cnpya, L1a or L2a) or carboxamides (2-cnpyb or L1b). An auxiliary ligand, namely syn-2-pyridinealdoxime or pyridine, acting cooperatively with the metal ion (CuII in this case), induced an E/Z isomerization of the H2L4 ligand; the E- and Z-isomers were isolated separately and fully characterized (compounds 9 and 10, respectively). A one-pot activation of nitrile groups in different molecules was achieved in the syntheses of 8 and 9. Complexes 1–10 are catalyst precursors for the solvent-free microwave (MW)-assisted selective oxidation of secondary alcohols to the corresponding ketones, with typical yields in the 29–99% range (TOFs up to 4.94 × 103 h–1) after 30 min of MW irradiation.