Abstract
[Os(phen)(RaaiR′) 2](PF 6) 2 [phen = 1,10-phenanthroline, RaaiR′ = 1-alkyl-2-(arylazo)imidazole, p-R–C 6H 4–N N–C 3H 2–NN–1-R′, where R = H ( a), Me ( b), Cl ( c) and R′ = Me ( 2), Et ( 3), CH 2Ph ( 4) have been synthesized from the reaction of cis– trans– cis-[OsBr 2(RaaiR′) 2] with phen in the presence of aqueous AgNO 3 in ethanol. The structure of [Os(phen)(ClaaiEt) 2](PF 6) 2 was confirmed by X-ray diffraction study. Electronic spectra exhibit a strong MLCT band at 490–512 nm along with weak transition at longer wavelength 865–880 nm. Cyclic voltammetry of the complexes shows two metal redox couples, Os(III)/Os(II) at 0.9–1.0 V and Os(IV)/Os(III) at 1.4–1.6 V versus SCE, and three successive ligand reductions. The EHMO calculation using crystallographic parameters of the complex has been compared with analogous Ru and Os complexes. A correlation between electronic properties and MO results is also reported.
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