Complex Series Ru(tpy)(dpk)(X)n+ (tpy = 2,2': 6',2''-Terpyridine; dpk = 2,2'-Dipyridyl Ketone; X = Cl-, CH3CN, NO2-, NO+, NO.bul., NO-): Substitution and Electron Transfer, Structure, and Spectroscopy

, , , , , , , und . Inorganic Chemistry 44 (17): 6092--6099 (2005)


The complex framework Ru(tpy)(dpk)2+ (tpy = 2,2':6',2''-terpyridine, dpk = 2,2'-dipyridyl ketone) was used to study the generation and reactivity of the nitrosyl complex Ru(tpy)(dpk)(NO)3+ (43+). Stepwise conversion of the chloro complex Ru(tpy)(dpk)(Cl)+ (1+) via Ru(tpy)(dpk)(MeCN)2+ (22+) and the nitro compd. Ru(tpy)(dpk)(NO2)+ (3+) yielded 43+; all four complexes were structurally characterized as perchlorates. Electrochem. oxidn. and redn. were studied as a function of the monodentate ligand as were the IR and UV-visible spectroscopic responses (absorption/emission). The kinetics of the nitroso-to-nitro conversion 43+/3+ in aq. environment were also studied. Two-step redn. of 43+ was monitored via EPR, UV-visible, and IR (n(NO), n(CO)) spectroelectrochem. to confirm the RuNO7 configuration of 42+ and to exhibit a relatively intense band at 505 nm for 4+, attributed to a ligand-to-ligand transition originating from bound NO-. on SciFinder(R)

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