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)
%0 Journal Article
%1 Sarkar.2005b
%A Sarkar, Sounak
%A Sarkar, Biprajit
%A Chanda, Nripen
%A Kar, Sanjib
%A Mobin, Shaikh M.
%A Fiedler, Jan
%A Kaim, Wolfgang
%A Lahiri, Goutam Kumar.
%D 2005
%J Inorganic Chemistry
%K anion cation complex complex;nitrosyl dipyridyl electrochem ketone ligand nitroso nitrosyl oxidn precursor;kinetics prepn radical reactivity redox ruthenium terpyridine
%N 17
%P 6092--6099
%R 10.1021/ic050533e
%T 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
%V 44
%X 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)
@article{Sarkar.2005b,
abstract = {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+ ([4]3+). Stepwise conversion of the chloro complex [Ru(tpy)(dpk)(Cl)]+ ([1]+) via [Ru(tpy)(dpk)(MeCN)]2+ ([2]2+) and the nitro compd. [Ru(tpy)(dpk)(NO2)]+ ([3]+) yielded [4]3+; 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 [4]3+/[3]+ in aq. environment were also studied. Two-step redn. of [4]3+ was monitored via EPR, UV-visible, and IR (\textgreek{n}(NO), \textgreek{n}(CO)) spectroelectrochem. 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-. [on SciFinder(R)]},
added-at = {2018-08-09T10:59:25.000+0200},
author = {Sarkar, Sounak and Sarkar, Biprajit and Chanda, Nripen and Kar, Sanjib and Mobin, Shaikh M. and Fiedler, Jan and Kaim, Wolfgang and Lahiri, Goutam Kumar.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2fc43475cc109889bb85956b19cb03e2e/galaktoze},
doi = {10.1021/ic050533e},
interhash = {782ae3f55e983dd19539e0430e63537b},
intrahash = {fc43475cc109889bb85956b19cb03e2e},
issn = {0020-1669},
journal = {Inorganic Chemistry},
keywords = {anion cation complex complex;nitrosyl dipyridyl electrochem ketone ligand nitroso nitrosyl oxidn precursor;kinetics prepn radical reactivity redox ruthenium terpyridine},
number = 17,
pages = {6092--6099},
timestamp = {2018-08-09T13:02:07.000+0200},
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.bul., NO-): Substitution and Electron Transfer, Structure, and Spectroscopy},
volume = 44,
year = 2005
}