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Abstract: The reaction of 1-alkyl-2-{(o-thioalkyl)phenylazo}imidazoles (SRaaiNR) (2a/2b) with Ru(II) has synthesized [Ru(SRaaiNR)2](ClO4)2 (3a/3b) in 2-methoxyethanol. The reaction in methanol, however, has synthesized [Ru(SRaaiNR)( S RaaiNR)Cl](ClO4) (4a/4b). The solid phase reaction of SRaaiNR and RuCl3 on silica gel surface upon microwave irradiation has synthesized [Ru(SRaaiNR)(SaaiNR)](PF6) (5a/5b) [SRaaiNR represents tridentate N,N′,S-chelator; S RaaiNR is N,N′-bidentate chelator where S does not coordinate and SaaiNR refers N,N′,S-chelator where S refers to thiolato binding]. The structural characterization of [Ru(SEtaaiNEt)( S EtaaiNEt)Cl](ClO4) (4b) and [Ru(SEtaaiNEt)(SaaiNEt)](PF6) (5b) has been confirmed by single crystal X-ray diffraction study. The IR, UV–Vis, and 1H NMR spectral data also support the stereochemistry of the complexes. The complexes show metal oxidation, Ru(III)/Ru(II), and ligand reductions (azo/azo−, azo−/azo ). The molecular orbital diagram has been drawn by density functional theory (DFT) calculation. Normal mode of analysis has been performed to correlate calculated and experimental frequencies of representative complexes. The electronic movement and assignment of electronic spectra have been carried out by TDDFT calculation both in gas and acetonitrile phase. [Copyright &y& Elsevier]

Abstract: trans-(Cl)-[Ru(CO)2Cl2(PaiR/TaiR)] compounds have been synthesized by reacting 1-alkyl-2-(phenylazo)imidazole (PaiR) or 1-alkyl-2-(p-tolylazo)imidazoles (TaiR) with [Ru(CO)2Cl2] n in methanol under refluxing conditions. The X-ray crystallographic study of trans-(Cl)-[Ru(CO)2Cl2(PaiEt)] (PaiEt=1-ethyl-2-(phenylazo)imidazole) shows a distorted octahedral geometry with a trans-Cl,Cl configuration. An intermolecular hydrogen bonded dimer serves as a motif in the supramolecular network with C–H⋯π and π⋯π interactions. The complexes show metal oxidation, Ru(III)/Ru(II); and reduction of the coordinated azo (–N) function. The molecular orbital diagram has been drawn by density functional theory (DFT) using an optimized geometry from the single crystal X-ray parameters. The electronic movement and assignment of electronic spectra have been carried out by TD-DFT calculations both in the gas and acetonitrile phase. [Copyright &y& Elsevier]