Cyclic voltammetric and fiber-optic infrared spectroelectrochemical studies of six-coordinate (por)Ru(NO)Cl compounds (por = porphyrinato dianion)

Abstract

The redox behavior of representative (por)Ru(NO)Cl complexes (por=OEP, T(p-OMe)PP, T(p-CF3)PP) have been obtained. The compounds possess linear RuNO moieties as exemplified by the X-ray crystal structure of (T(p-OMe)PP)Ru(NO)Cl (Ru–N–O=174(2)°, Ru–N(O)=1.790(17)Å, Ru–Cl=2.220(6)Å). The first electrooxidations of the (por)Ru(NO)Cl compounds in CH2Cl2 occur in the order OEP (+0.51V)<T(p-OMe)PP (+0.57V)<T(p-CF3)PP (+0.84V) (versus Fc/Fc+). We have utilized infrared reflectance spectroelectrochemistry to determine that the first oxidations are porphyrin centered. In addition, the reductions are largely RuNO centered.