What determines the comproportionation constant in molecule-bridged mixed-valence complexes? Evidence for the crucial role of the ligand LUMO in four ruthenium(II)ruthenium(III) dimers
Electrochem. data of 4 bis chelate bridged complexes Ru(bpy)22(μ, η4-L)n+ (bpy = 2,2'-bipyridine, L = sym. N heterocycle such as 3,6-di-2-pyridyl-1,2,4,5-tetrazine, 2,5-di-2-pyridylpyrazine, 2,2'-bipyrimidine or azo-2,2'-bipyridine) show conclusively that the electron d. at the coordination centers in the LUMO of the bridging p ligand dets. the comproportionation const. of the RuIIRuIII mixed-valence state (n = 5). Neither the no. of mediating p centers nor the distance or the orientation of the 2 metal centers plays a significant role. The presence of 2 equiv chiral metal centers in these complexes leads to formation of meso and DL diastereomers, as shown for one example by 1H NMR. on SciFinder(R)
%0 Journal Article
%1 Ernst.1988c
%A Ernst, Sylvia
%A Kasack, Volker
%A Kaim, Wolfgang.
%D 1988
%J Inorganic Chemistry
%K azobipyridine bipyridine complex complex;LUMO complex;electron complex;pyridylpyrazine comproportionation;comproportionation comproportionation;pyridyltetrazine comproportionation;sym comproportionation;voltammetry density dinuclear heterocycle mixed nitrogen ruthenium valent voltammetry
%N 7
%P 1146--1148
%R 10.1021/ic00280a010
%T What determines the comproportionation constant in molecule-bridged mixed-valence complexes? Evidence for the crucial role of the ligand LUMO in four ruthenium(II)ruthenium(III) dimers
%V 27
%X Electrochem. data of 4 bis chelate bridged complexes Ru(bpy)22(μ, η4-L)n+ (bpy = 2,2'-bipyridine, L = sym. N heterocycle such as 3,6-di-2-pyridyl-1,2,4,5-tetrazine, 2,5-di-2-pyridylpyrazine, 2,2'-bipyrimidine or azo-2,2'-bipyridine) show conclusively that the electron d. at the coordination centers in the LUMO of the bridging p ligand dets. the comproportionation const. of the RuIIRuIII mixed-valence state (n = 5). Neither the no. of mediating p centers nor the distance or the orientation of the 2 metal centers plays a significant role. The presence of 2 equiv chiral metal centers in these complexes leads to formation of meso and DL diastereomers, as shown for one example by 1H NMR. on SciFinder(R)
@article{Ernst.1988c,
abstract = {Electrochem. data of 4 bis chelate bridged complexes {[Ru(bpy)2]2(μ, η4-L)}n+ (bpy = 2,2'-bipyridine, L = sym. N heterocycle such as 3,6-di-2-pyridyl-1,2,4,5-tetrazine, 2,5-di-2-pyridylpyrazine, 2,2'-bipyrimidine or azo-2,2'-bipyridine) show conclusively that the electron d. at the coordination centers in the LUMO of the bridging \textgreek{p} ligand dets. the comproportionation const. of the RuIIRuIII mixed-valence state (n = 5). Neither the no. of mediating \textgreek{p} centers nor the distance or the orientation of the 2 metal centers plays a significant role. The presence of 2 equiv chiral metal centers in these complexes leads to formation of meso and DL diastereomers, as shown for one example by 1H NMR. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Ernst, Sylvia and Kasack, Volker and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/299b300f3415ae63df8e73244441279dd/b_schwederski},
doi = {10.1021/ic00280a010},
interhash = {1c9f5bb409e2cf5c26cf63b9bab8aab6},
intrahash = {99b300f3415ae63df8e73244441279dd},
issn = {0020-1669},
journal = {Inorganic Chemistry},
keywords = {azobipyridine bipyridine complex complex;LUMO complex;electron complex;pyridylpyrazine comproportionation;comproportionation comproportionation;pyridyltetrazine comproportionation;sym comproportionation;voltammetry density dinuclear heterocycle mixed nitrogen ruthenium valent voltammetry},
number = 7,
pages = {1146--1148},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {What determines the comproportionation constant in molecule-bridged mixed-valence complexes? Evidence for the crucial role of the ligand LUMO in four ruthenium(II)ruthenium(III) dimers},
volume = 27,
year = 1988
}