Azo compounds as electron acceptor or radical ligands in transition metal species: Spectroelectrochemistry and high-field EPR studies of ruthenium, rhodium and copper complexes of 2,2'-azobis(5-chloropyrimidine)
Oxidative coupling of 2-aminopyrimidine with LiOCl produces 5-chloro-2,2'-azobis(pyrimidine) and 2,2'-azobis(5-chloropyrimidine) (abcp), both of which were structurally characterized. The sym. abcp was used as strongly p-accepting mono- and bis-chelate ligand in complexes with (bpy)2Ru2+, (H6C6)ClRu+, (Ph3P)2Cu+ and (OC)3ClRe. The p-acceptor capability of abcp results in low-energy MLCT transitions and facile redn. to isolable radical complexes of which the DFT-calcd. and structurally characterized dicopper(I) species (μ-abcp)Cu(PPh3)22(PF6) was studied by X- and W-band EPR and (μ-abcp)Ru(bpy)22(PF6)3 at 9.6, 230 and 285 GHz EPR frequency. The results indicate considerable metal-ligand orbital mixing in the singly occupied MOs. on SciFinder(R)
%0 Journal Article
%1 Kaim.2003
%A Kaim, Wolfgang
%A Doslik, Natasa
%A Frantz, Stephanie
%A Sixt, Torsten
%A Wanner, Matthias
%A Baumann, Frank
%A Denninger, Gert
%A Kummerer, Hans-Jurrgen
%A Duboc-Toia, Carole
%A Fiedler, Jan
%A Zalis, Stanislav.
%D 2003
%J Journal of Molecular Structure
%K ESR azochloropyrimidine azochloropyrimidine;transition chloroazopyrimidine;electrochem crystal cyclic metal oxidn prepn redn spectroelectrochem structure transition voltammetry
%N 1-3
%P 183--194
%R 10.1016/S0022-2860(03)00339-9
%T Azo compounds as electron acceptor or radical ligands in transition metal species: Spectroelectrochemistry and high-field EPR studies of ruthenium, rhodium and copper complexes of 2,2'-azobis(5-chloropyrimidine)
%V 656
%X Oxidative coupling of 2-aminopyrimidine with LiOCl produces 5-chloro-2,2'-azobis(pyrimidine) and 2,2'-azobis(5-chloropyrimidine) (abcp), both of which were structurally characterized. The sym. abcp was used as strongly p-accepting mono- and bis-chelate ligand in complexes with (bpy)2Ru2+, (H6C6)ClRu+, (Ph3P)2Cu+ and (OC)3ClRe. The p-acceptor capability of abcp results in low-energy MLCT transitions and facile redn. to isolable radical complexes of which the DFT-calcd. and structurally characterized dicopper(I) species (μ-abcp)Cu(PPh3)22(PF6) was studied by X- and W-band EPR and (μ-abcp)Ru(bpy)22(PF6)3 at 9.6, 230 and 285 GHz EPR frequency. The results indicate considerable metal-ligand orbital mixing in the singly occupied MOs. on SciFinder(R)
@article{Kaim.2003,
abstract = {Oxidative coupling of 2-aminopyrimidine with LiOCl produces 5-chloro-2,2'-azobis(pyrimidine) and 2,2'-azobis(5-chloropyrimidine) (abcp), both of which were structurally characterized. The sym. abcp was used as strongly \textgreek{p}-accepting mono- and bis-chelate ligand in complexes with [(bpy)2Ru]2+, [(H6C6)ClRu]+, [(Ph3P)2Cu]+ and (OC)3ClRe. The \textgreek{p}-acceptor capability of abcp results in low-energy MLCT transitions and facile redn. to isolable radical complexes of which the DFT-calcd. and structurally characterized dicopper(I) species {(μ-abcp)[Cu(PPh3)2]2}(PF6) was studied by X- and W-band EPR and {(μ-abcp)[Ru(bpy)2]2}(PF6)3 at 9.6, 230 and 285 GHz EPR frequency. The results indicate considerable metal-ligand orbital mixing in the singly occupied MOs. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Kaim, Wolfgang and Doslik, Natasa and Frantz, Stephanie and Sixt, Torsten and Wanner, Matthias and Baumann, Frank and Denninger, Gert and Kummerer, Hans-Jurrgen and Duboc-Toia, Carole and Fiedler, Jan and Zalis, Stanislav.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2cccf0610261c097bb1c9cc8cd246d6de/huebleriac},
doi = {10.1016/S0022-2860(03)00339-9},
interhash = {a122261c910c5e1e550214967196ce0f},
intrahash = {cccf0610261c097bb1c9cc8cd246d6de},
issn = {0022-2860},
journal = {Journal of Molecular Structure},
keywords = {ESR azochloropyrimidine azochloropyrimidine;transition chloroazopyrimidine;electrochem crystal cyclic metal oxidn prepn redn spectroelectrochem structure transition voltammetry},
number = {1-3},
pages = {183--194},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Azo compounds as electron acceptor or radical ligands in transition metal species: Spectroelectrochemistry and high-field EPR studies of ruthenium, rhodium and copper complexes of 2,2'-azobis(5-chloropyrimidine)},
volume = 656,
year = 2003
}