Synthesis, characterization, electronic structure and catalytic activity of new ruthenium carbonyl complexes of N-((2-pyridyl)methylidene)-2-aminothiazole

Abstract Reaction of ruthenium carbonyls, [Ru(CO) 2 Cl 2 ] n /[Ru(CO) 4 I 2 ] with bidentate Schiffs base ligands derived by the condensation of pyridine-2-carboxaldehyde with 2-aminothiazole in a 1:1 mole ratio in acetonitrile led to the formation of complexes having general formula [Ru(CO) 2 (L)X 2 ] (X = Cl ( 1 ) and I ( 2 )) ( L  = N-[(2-pyridyl)methylidene]-2-aminothiazole). The compounds have been characterized by various analytical and spectroscopic (IR, electronic and 1 H NMR) studies. In acetonitrile solution the complexes exhibit a weak broad metal–ligand to ligand charge transfer (MLLCT) band along with ILCT transitions. The compounds are emissive in room temperature upon excitation in the ILCT band. The complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 1.44 V for 1 and 0.94 V for 2 . Catalytic activity of these compounds is investigated to the oxidation of PhCH 2 OH to PhCHO, 2-butanol (C 4 H 9 OH) to 2-butanone, 1-phenylethanol (PhC 2 H 4 OH) to acetophenone, cyclopentanol (C 5 H 9 OH) to cyclopentanone, cyclohexanol to cyclohexanone, cycloheptanol to cycloheptanone and cycloctanol to cycloctanone using N-methylmorpholine-N-oxide (NMO) as oxidant. The catalytic efficiency of 2 is greater than complex 1 and well correlate with the metal oxidation potential of the complexes. DFT, NBO and TDDFT calculations are employed to explain the structural and electronic features and to support the spectroscopic assignments.