Coordination of substitutionally inert Ru(bpy)22+ fragments (bpy = 2,2'-bipyridine) to the a-iminoketone chelate ligands pyrazine-2-dimethylcarboxamide (L) and 4,7-phenanthroline-5,6-dione (HL') yields Ru(bpy)2(L-N,O)2+, Ru(bpy)2(L'-O,O')+, and ((L'-N,O;N',O')Ru(bpy)224+ which exhibit a rich electrochem. The distinctly different electronic structures of the complexes are evident from the ESR behavior of paramagnetic intermediates: N,O-coordinated complexes have the unpaired electron residing in the ligand p system upon redn., albeit with g \textless2 for the complex of L but with g \textgreater2 for the binuclear complex of HL'. The paramagnetic O,O'-coordinated mononuclear complex with (L') has its redox potentials shifted pos. relative to that of the binuclear system. These results are particularly noteworthy because L and HL' can be regarded as model compds. for the flavin and methoxatin dehydrogenase cofactors. on SciFinder(R)
%0 Journal Article
%1 Ernst.1987
%A Ernst, Sylvia
%A Kasack, Volker
%A Bessenbacher, Christian
%A Kaim, Wolfgang.
%D 1987
%J Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences
%K bipyridine cofactor complex;electrochem dehydrogenase model phenanthrolinedione phenanthrolinedione;ruthenium pyrazinecarboxamide ruthenium
%N 4
%P 425--430
%R 10.1515/znb-1987-0407
%T Mono- and binuclear bis(2,2'-bipyridine)ruthenium complexes with N,O-ligands modeling dehydrogenase cofactors
%V 42
%X Coordination of substitutionally inert Ru(bpy)22+ fragments (bpy = 2,2'-bipyridine) to the a-iminoketone chelate ligands pyrazine-2-dimethylcarboxamide (L) and 4,7-phenanthroline-5,6-dione (HL') yields Ru(bpy)2(L-N,O)2+, Ru(bpy)2(L'-O,O')+, and ((L'-N,O;N',O')Ru(bpy)224+ which exhibit a rich electrochem. The distinctly different electronic structures of the complexes are evident from the ESR behavior of paramagnetic intermediates: N,O-coordinated complexes have the unpaired electron residing in the ligand p system upon redn., albeit with g \textless2 for the complex of L but with g \textgreater2 for the binuclear complex of HL'. The paramagnetic O,O'-coordinated mononuclear complex with (L') has its redox potentials shifted pos. relative to that of the binuclear system. These results are particularly noteworthy because L and HL' can be regarded as model compds. for the flavin and methoxatin dehydrogenase cofactors. on SciFinder(R)
@article{Ernst.1987,
abstract = {Coordination of substitutionally inert [Ru(bpy)2]2+ fragments (bpy = 2,2'-bipyridine) to the \textgreek{a}-iminoketone chelate ligands pyrazine-2-dimethylcarboxamide (L) and 4,7-phenanthroline-5,6-dione (HL') yields [Ru(bpy)2(L-N,O)]2+, [Ru(bpy)2(L'-O,O')]+, and ((L'-N,O;N',O')[Ru(bpy)2]24+ which exhibit a rich electrochem. The distinctly different electronic structures of the complexes are evident from the ESR behavior of paramagnetic intermediates: N,O-coordinated complexes have the unpaired electron residing in the ligand \textgreek{p} system upon redn., albeit with g {\textless}2 for the complex of L but with g {\textgreater}2 for the binuclear complex of HL'. The paramagnetic O,O'-coordinated mononuclear complex with (L') has its redox potentials shifted pos. relative to that of the binuclear system. These results are particularly noteworthy because L and HL' can be regarded as model compds. for the flavin and methoxatin dehydrogenase cofactors. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Ernst, Sylvia and Kasack, Volker and Bessenbacher, Christian and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/23d033638d45707c15028d6684a52332f/huebleriac},
doi = {10.1515/znb-1987-0407},
interhash = {1b09bea95462e65f8a3887a0754cf940},
intrahash = {3d033638d45707c15028d6684a52332f},
issn = {0932-0776},
journal = {Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences},
keywords = {bipyridine cofactor complex;electrochem dehydrogenase model phenanthrolinedione phenanthrolinedione;ruthenium pyrazinecarboxamide ruthenium},
number = 4,
pages = {425--430},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Mono- and binuclear bis(2,2'-bipyridine)ruthenium complexes with N,O-ligands modeling dehydrogenase cofactors},
volume = 42,
year = 1987
}