title: Complex series [Ru(tpy)(dpk)(X)]n+ (tpy = 2,2':6',2''-terpyridine; dpk = 2,2'-dipyridyl ketone; X = Cl-, CH3CN, NO2(-), NO+, NO*, NO-): substitution and electron transfer, structure, and spectroscopy.
abstract: The complex framework [Ru(tpy)(dpk)]2+ has been used to study the generation and reactivity of the nitrosyl complex [Ru(tpy)(dpk)(NO)]3+ ([4]3+). Stepwise conversion of the chloro complex [Ru(tpy)(dpk)(Cl)]+ ([1]+) via [Ru(tpy)(dpk)(CH3CN)]2+ ([2]2+) and the nitro compound [Ru(tpy)(dpk)(NO2)]+ ([3]+) yielded [4]3+; all four complexes were structurally characterized as perchlorates. Electrochemical oxidation and reduction was investigated as a function of the monodentate ligand as was the IR and UV-vis spectroscopic response (absorption/emission). The kinetics of the conversion [4]3+/[3]+ in aqueous environment were also studied. Two-step reduction of [4]3+ was monitored via EPR, UV-vis, and IR (nu(NO), nu(CO)) spectroelectrochemistry to confirm the {RuNO}7 configuration of [4]2+ and to exhibit a relatively intense band at 505 nm for [4]+, attributed to a ligand-to-ligand transition originating from bound NO-.
authors.affiliation: Department of Chemistry, Indian Institute of Technology-Bombay, Powai, Mumbai-400076, India.
authors.forename: Sounak
authors.initials: S
authors.lastname: Sarkar
authors.forename: Biprajit
authors.initials: B
authors.lastname: Sarkar
authors.forename: Nripen
authors.initials: N
authors.lastname: Chanda
authors.forename: Sanjib
authors.initials: S
authors.lastname: Kar
authors.forename: Shaikh M
authors.initials: SM
authors.lastname: Mobin
authors.forename: Jan
authors.initials: J
authors.lastname: Fiedler
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Kaim
authors.forename: Goutam Kumar
authors.initials: GK
authors.lastname: Lahiri
mesh_terms: D018360:Crystallography, X-Ray; D004563:Electrochemistry; D004579:Electron Transport; D008956:Models, Chemical; D015394:Molecular Structure; D017975:Ruthenium Compounds / Q000737:chemistry*; D013057:Spectrum Analysis
chemical_list: D017975:Ruthenium Compounds