The redox pair (m-abcp)Cu(dppf)22+/+ (abcp = 2,2'-azobis(5-chloropyrimidine) and dppf = 1,1'-bis(diphenylphosphino)ferrocene) was structurally characterized to reveal the lengthening of the NN and shortening of the CNazo bonds on redn., each by $\sim$0.04 \AA. These and other charge forms, (m-abcp)Cu(dppf)2n+ (n = 0, 3+, 4+), were studied spectroelectrochem. (UV-visible-near-IR, EPR) to reveal an abcp-based 2nd redn. and a stepwise ferrocene-centered oxidn. of the 2+ precursor. In contrast to the small but detectable comproportionation const. of Kc = 17 for the Fc/Fc+ mixed-valence (3+) charge state, the monocationic radical complex exhibits a very large Kc value of 1016. on SciFinder(R)
%0 Journal Article
%1 Jana.2013
%A Jana, Rajkumar
%A Lissner, Falk
%A Schwederski, Brigitte
%A Fiedler, Jan
%A Kaim, Wolfgang.
%D 2013
%J Organometallics
%K azobispyrimidine bridging complex complex;heterotetranuclear copper crystal diphosphinoferrocenyl electrochem;mol heterotetranuclear iron phosphinoferrocenyl prepn structure
%N 20
%P 5879--5886
%R 10.1021/om400466u
%T A Ligand-Bridged Heterotetranuclear (Fe2Cu2) Redox System with Fc/Fc+ and Radical Ion Intermediates
%V 32
%X The redox pair (m-abcp)Cu(dppf)22+/+ (abcp = 2,2'-azobis(5-chloropyrimidine) and dppf = 1,1'-bis(diphenylphosphino)ferrocene) was structurally characterized to reveal the lengthening of the NN and shortening of the CNazo bonds on redn., each by $\sim$0.04 \AA. These and other charge forms, (m-abcp)Cu(dppf)2n+ (n = 0, 3+, 4+), were studied spectroelectrochem. (UV-visible-near-IR, EPR) to reveal an abcp-based 2nd redn. and a stepwise ferrocene-centered oxidn. of the 2+ precursor. In contrast to the small but detectable comproportionation const. of Kc = 17 for the Fc/Fc+ mixed-valence (3+) charge state, the monocationic radical complex exhibits a very large Kc value of 1016. on SciFinder(R)
@article{Jana.2013,
abstract = {The redox pair [(\textgreek{m}-abcp){Cu(dppf)}2]2+/+ (abcp = 2,2'-azobis(5-chloropyrimidine) and dppf = 1,1'-bis(diphenylphosphino)ferrocene) was structurally characterized to reveal the lengthening of the NN and shortening of the CNazo bonds on redn., each by $\sim$0.04 {\AA}. These and other charge forms, [(\textgreek{m}-abcp){Cu(dppf)}2]n+ (n = 0, 3+, 4+), were studied spectroelectrochem. (UV-visible-near-IR, EPR) to reveal an abcp-based 2nd redn. and a stepwise ferrocene-centered oxidn. of the 2+ precursor. In contrast to the small but detectable comproportionation const. of Kc = 17 for the Fc/Fc+ mixed-valence (3+) charge state, the monocationic radical complex exhibits a very large Kc value of 1016. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Jana, Rajkumar and Lissner, Falk and Schwederski, Brigitte and Fiedler, Jan and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/27ee222e8a6b6fdb2f67e54004e92c96a/huebleriac},
doi = {10.1021/om400466u},
interhash = {1eba7bcbd31ff5c83276069de605b691},
intrahash = {7ee222e8a6b6fdb2f67e54004e92c96a},
issn = {0276-7333},
journal = {Organometallics},
keywords = {azobispyrimidine bridging complex complex;heterotetranuclear copper crystal diphosphinoferrocenyl electrochem;mol heterotetranuclear iron phosphinoferrocenyl prepn structure},
number = 20,
pages = {5879--5886},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {A Ligand-Bridged Heterotetranuclear (Fe2Cu2) Redox System with Fc/Fc+ and Radical Ion Intermediates},
volume = 32,
year = 2013
}
