The compds. Ru(acac)2(L) (1) and Ru2(acac)4(m-L) (2) with acac- = acetylacetonato and L = thioindigo were characterized crystallog. with a cis-configurated L and O,O'-coordinated metal in 1 and with trans-configurated L and two S,O-coordinated bridged ruthenium centers for 2. The electronic structures of 1 and 2 were confirmed by spectroscopy and d. functional theory calcns., suggesting considerable metal-to-ligand electron transfer resulting in the formation of the thioindigo radical anion and oxidized metal(s). UV-Vis-Near-IR and IR (spectro)electrochem. was used to investigate charged forms 1n (n = 1+, 1-) and 2n (n = 1+, 1-, 2-), which reveal electron transfer activity of both the metal and the thioindigo ligand as well as sizable orbital mixing. An intense near-IR absorption is obsd. for 2- at 2180 nm. The remarkable ligand properties of thioindigo are being discussed in connection to related coordination compds. of indigo derivs. such as dehydroindigo and corresponding (\dqNindigo\dq) diimines. on SciFinder(R)
%0 Journal Article
%1 Chatterjee.2018b
%A Chatterjee, Madhumita
%A Mondal, Sudipta
%A Ghosh, Prabir
%A Kaim, Wolfgang
%A Lahiri, Goutam Kumar.
%D 2018
%J Inorganic Chemistry
%K ESR acetylacetonato complex crystal electrochem electronic prepn ruthenium structure structures thioindigo thioindigo;ruthenium
%N 19
%P 12187--12194
%R 10.1021/acs.inorgchem.8b01829
%T Mononuclear and Dinuclear Ruthenium Complexes of cis- and trans-Thioindigo: Geometrical and Electronic Structure Analyses
%V 57
%X The compds. Ru(acac)2(L) (1) and Ru2(acac)4(m-L) (2) with acac- = acetylacetonato and L = thioindigo were characterized crystallog. with a cis-configurated L and O,O'-coordinated metal in 1 and with trans-configurated L and two S,O-coordinated bridged ruthenium centers for 2. The electronic structures of 1 and 2 were confirmed by spectroscopy and d. functional theory calcns., suggesting considerable metal-to-ligand electron transfer resulting in the formation of the thioindigo radical anion and oxidized metal(s). UV-Vis-Near-IR and IR (spectro)electrochem. was used to investigate charged forms 1n (n = 1+, 1-) and 2n (n = 1+, 1-, 2-), which reveal electron transfer activity of both the metal and the thioindigo ligand as well as sizable orbital mixing. An intense near-IR absorption is obsd. for 2- at 2180 nm. The remarkable ligand properties of thioindigo are being discussed in connection to related coordination compds. of indigo derivs. such as dehydroindigo and corresponding (\dqNindigo\dq) diimines. on SciFinder(R)
@article{Chatterjee.2018b,
abstract = {The compds. [Ru(acac)2(L)] (1) and [Ru2(acac)4(\textgreek{m}-L)] (2) with acac- = acetylacetonato and L = thioindigo were characterized crystallog. with a cis-configurated L and O,O'-coordinated metal in 1 and with trans-configurated L and two S,O-coordinated bridged ruthenium centers for 2. The electronic structures of 1 and 2 were confirmed by spectroscopy and d. functional theory calcns., suggesting considerable metal-to-ligand electron transfer resulting in the formation of the thioindigo radical anion and oxidized metal(s). UV-Vis-Near-IR and IR (spectro)electrochem. was used to investigate charged forms 1n (n = 1+, 1-) and 2n (n = 1+, 1-, 2-), which reveal electron transfer activity of both the metal and the thioindigo ligand as well as sizable orbital mixing. An intense near-IR absorption is obsd. for 2- at 2180 nm. The remarkable ligand properties of thioindigo are being discussed in connection to related coordination compds. of indigo derivs. such as dehydroindigo and corresponding ({\dq}Nindigo{\dq}) diimines. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Chatterjee, Madhumita and Mondal, Sudipta and Ghosh, Prabir and Kaim, Wolfgang and Lahiri, Goutam Kumar.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/242d0e0507dd020a0cc1d8bcf6845a5c3/b_schwederski},
doi = {10.1021/acs.inorgchem.8b01829},
interhash = {78798094d91b3bdfcbdee504687c1d21},
intrahash = {42d0e0507dd020a0cc1d8bcf6845a5c3},
issn = {0020-1669},
journal = {Inorganic Chemistry},
keywords = {ESR acetylacetonato complex crystal electrochem electronic prepn ruthenium structure structures thioindigo thioindigo;ruthenium},
number = 19,
pages = {12187--12194},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Mononuclear and Dinuclear Ruthenium Complexes of cis- and trans-Thioindigo: Geometrical and Electronic Structure Analyses},
volume = 57,
year = 2018
}
