In contrast to several reported coordination compds. of trans-Nindigo ligands Nindigo = indigo-bis(N-phenylimine) = LH2 with one or two six-membered chelate rings involving one indole N and one extracyclic N for metal binding, the new diruthenium complex ion (acac)2Ru(m,h2:h2-L)Ru(bpy)22+ = (2)2+ exhibits edge-sharing five- and seven-membered chelate rings in the 1st documented case of asym. bridging by a Nindigo ligand in the cis configuration L2- = indigo-bis(N-phenylimine)dianion. The dication in 2(ClO4)2 displays one Ru(a-diimine)3 site and one Ru center with three neg. charged chelate ligands. 2(ClO4)2 was obtained from the Ru(bpy)22+ contg. cis precursor (LH)Ru(bpy)2ClO4 = 1ClO4, which exhibits cation intramol. H-bonding. Four accessible oxidn. states each were characterized for the 1n and 2n redox series with respect to metal- or ligand-centered electron transfer, based on x-ray structures, ESR, and UV-visible-near-IR spectroelectrochem. in conjunction with d. functional theory calcn. results. The structural asymmetry in the RuIII/RuII system 22+ is reflected by the electronic asymmetry (class I mixed-valence situation), leaving the noninnocent Nindigo bridge as the main redox-active site. on SciFinder(R)
%0 Journal Article
%1 Mondal.2014e
%A Mondal, Prasenjit
%A Plebst, Sebastian
%A Ray, Ritwika
%A Mobin, Shaikh M.
%A Kaim, Wolfgang
%A Lahiri, Goutam Kumar.
%D 2014
%J Inorganic Chemistry
%K acac bipyridine crystal dinuclear;ruthenium electron electronic mononuclear noninnocent phenylimineindigo prepn ruthenium spectroelectrochem structure transfer
%N 17
%P 9348--9356
%R 10.1021/ic501460d
%T Uncommon cis Configuration of a Metal-Metal Bridging Noninnocent Nindigo Ligand
%V 53
%X In contrast to several reported coordination compds. of trans-Nindigo ligands Nindigo = indigo-bis(N-phenylimine) = LH2 with one or two six-membered chelate rings involving one indole N and one extracyclic N for metal binding, the new diruthenium complex ion (acac)2Ru(m,h2:h2-L)Ru(bpy)22+ = (2)2+ exhibits edge-sharing five- and seven-membered chelate rings in the 1st documented case of asym. bridging by a Nindigo ligand in the cis configuration L2- = indigo-bis(N-phenylimine)dianion. The dication in 2(ClO4)2 displays one Ru(a-diimine)3 site and one Ru center with three neg. charged chelate ligands. 2(ClO4)2 was obtained from the Ru(bpy)22+ contg. cis precursor (LH)Ru(bpy)2ClO4 = 1ClO4, which exhibits cation intramol. H-bonding. Four accessible oxidn. states each were characterized for the 1n and 2n redox series with respect to metal- or ligand-centered electron transfer, based on x-ray structures, ESR, and UV-visible-near-IR spectroelectrochem. in conjunction with d. functional theory calcn. results. The structural asymmetry in the RuIII/RuII system 22+ is reflected by the electronic asymmetry (class I mixed-valence situation), leaving the noninnocent Nindigo bridge as the main redox-active site. on SciFinder(R)
@article{Mondal.2014e,
abstract = {In contrast to several reported coordination compds. of trans-Nindigo ligands [Nindigo = indigo-bis(N-phenylimine) = LH2] with one or two six-membered chelate rings involving one indole N and one extracyclic N for metal binding, the new diruthenium complex ion [(acac)2Ru(\textgreek{m},\textgreek{h}2:\textgreek{h}2-L)Ru(bpy)2]2+ = (2)2+ exhibits edge-sharing five- and seven-membered chelate rings in the 1st documented case of asym. bridging by a Nindigo ligand in the cis configuration [L2- = indigo-bis(N-phenylimine)dianion]. The dication in [2](ClO4)2 displays one Ru(\textgreek{a}-diimine)3 site and one Ru center with three neg. charged chelate ligands. [2](ClO4)2 was obtained from the [Ru(bpy)2]2+ contg. cis precursor [(LH)Ru(bpy)2]ClO4 = [1]ClO4, which exhibits cation intramol. H-bonding. Four accessible oxidn. states each were characterized for the 1n and 2n redox series with respect to metal- or ligand-centered electron transfer, based on x-ray structures, ESR, and UV-visible-near-IR spectroelectrochem. in conjunction with d. functional theory calcn. results. The structural asymmetry in the RuIII/RuII system 22+ is reflected by the electronic asymmetry (class I mixed-valence situation), leaving the noninnocent Nindigo bridge as the main redox-active site. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Mondal, Prasenjit and Plebst, Sebastian and Ray, Ritwika and Mobin, Shaikh M. and Kaim, Wolfgang and Lahiri, Goutam Kumar.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/23f0a8309af359b6b9c7e5411a93708e3/b_schwederski},
doi = {10.1021/ic501460d},
interhash = {6ce18fb32c0095709233a68fd2ed3738},
intrahash = {3f0a8309af359b6b9c7e5411a93708e3},
issn = {0020-1669},
journal = {Inorganic Chemistry},
keywords = {acac bipyridine crystal dinuclear;ruthenium electron electronic mononuclear noninnocent phenylimineindigo prepn ruthenium spectroelectrochem structure transfer},
number = 17,
pages = {9348--9356},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Uncommon cis Configuration of a Metal-Metal Bridging Noninnocent Nindigo Ligand},
volume = 53,
year = 2014
}