1422158-12-0Relevant articles and documents
Use of a Ru/Os-CO-diiodide precursor to synthesize heteroleptic 1-alkyl-2-(arylazo)imidazole complexes: The structural characterization, electrochemistry and catalytic activity
Sarkar, Shyamal Kumar,Jana, Mahendra Sekhar,Mondal, Tapan Kumar,Sinha, Chittaranjan
, p. 246 - 254 (2013/04/23)
Trans-(I,I)-[MI2(CO)2(RaaiR′)] (M = Ru, Os) (RaaiR′ = 1-alkyl-2-(arylazo)imidazoles) complexes have been synthesized by the reaction of RaaiR′ and [Ru(CO)4I2] or [Os(CO)4I2] in acetonitrile solution and the complexes have been characterized by elemental analysis and spectral (FT-IR, UV-Vis, 1H NMR) data. The structural confirmation has been determined by single crystal X-ray diffraction of trans-(I,I)-[MI2(CO) 2(HaaiEt)] (M = Ru, 3b; Os, 5b) (HaaiEt = 1-ethyl-2-(phenylazo) imidazole) and has shown a distorted octahedral geometry with a trans-I,I and cis-CO, CO configuration. The complexes show a M(III)/M(II) couple and the reduction of the chelated azoimine ligand. These complexes act as catalysts in the oxidation of PhCH2OH to PhCHO, 2-butanol (C4H 9OH) to 2-butanone, cyclopentanol (C5H9OH) to cyclopentanone and cyclohexanol to cyclohexanone by N-methylmorpholine-N-oxide (NMO). The molecular orbital diagram has been drawn by density functional theory (DFT) using the optimized geometry from the single crystal X-ray parameters. The assignments of electronic spectra have been carried out by TD-DFT calculations both in the gas and acetonitrile phases.