(OC)3ClRe(abpy) (1) and [(OC)3ClRe]2(abpy) (2) with abpy = 2,2'-azobispyridine were structurally characterized and studied by spectroelectrochem. in the UV-visible and in the IR carbonyl stretching region. 1 Exhibits a s-cis/E/s-trans configurated abpy ligand with metal coordination to one pyridyl and one azo function and one nonbonding Re-N interaction at 3.293 \AA to the 2nd pyridyl N atom. The dinuclear 2 with two azoimine-coordinated metal centers is distinguished by the trans arrangement of the chloride ligands with respect to the Re2(m-abpy) plane, the Re-Re distance is 5.033(7) \AA. The azo bond lengths at 1.272(9) (1) and 1.304(10) A (2) indicate substantial p back donation from the Re(I) centers into the p*(abpy) orbital. Spectroelectrochem. reveals the successive occupation of the p*(abpy) orbital by electrons; metal-to-ligand charge transfer features are shifted to higher energies and carbonyl stretching bands to lower wavenumbers. The EPR spectra of both radical anion intermediates 1$\surd$- and 2$\surd$- are dominated by very similar 185,187Re hyperfine splitting, ruling out a mixed-valent formulation. The 2nd electron uptake is followed by the rapid loss of one chloride, leading to an unsym. species in the dinuclear system. [on SciFinder(R)]
%0 Journal Article
%1 Hartmann.2000b
%A Hartmann, H.
%A Scheiring, T.
%A Fiedler, J.
%A Kaim, W.
%D 2000
%J Journal of Organometallic Chemistry
%K azobispyridine carbonyl chloro chloro;electrochem chloro;rhenium crystal prepn redn rhenium spectroelectrochem structure
%N 2
%P 267--272
%R 10.1016/S0022-328X(00)00282-5
%T Structures and spectroelectrochemistry (UV-vis, IR, EPR) of complexes [(OC)3ClRe]n(abpy), n = 1, 2; abpy = 2,2'-azobispyridine
%V 604
%X (OC)3ClRe(abpy) (1) and [(OC)3ClRe]2(abpy) (2) with abpy = 2,2'-azobispyridine were structurally characterized and studied by spectroelectrochem. in the UV-visible and in the IR carbonyl stretching region. 1 Exhibits a s-cis/E/s-trans configurated abpy ligand with metal coordination to one pyridyl and one azo function and one nonbonding Re-N interaction at 3.293 \AA to the 2nd pyridyl N atom. The dinuclear 2 with two azoimine-coordinated metal centers is distinguished by the trans arrangement of the chloride ligands with respect to the Re2(m-abpy) plane, the Re-Re distance is 5.033(7) \AA. The azo bond lengths at 1.272(9) (1) and 1.304(10) A (2) indicate substantial p back donation from the Re(I) centers into the p*(abpy) orbital. Spectroelectrochem. reveals the successive occupation of the p*(abpy) orbital by electrons; metal-to-ligand charge transfer features are shifted to higher energies and carbonyl stretching bands to lower wavenumbers. The EPR spectra of both radical anion intermediates 1$\surd$- and 2$\surd$- are dominated by very similar 185,187Re hyperfine splitting, ruling out a mixed-valent formulation. The 2nd electron uptake is followed by the rapid loss of one chloride, leading to an unsym. species in the dinuclear system. [on SciFinder(R)]
@article{Hartmann.2000b,
abstract = {(OC)3ClRe(abpy) (1) and [(OC)3ClRe]2(abpy) (2) with abpy = 2,2'-azobispyridine were structurally characterized and studied by spectroelectrochem. in the UV-visible and in the IR carbonyl stretching region. 1 Exhibits a s-cis/E/s-trans configurated abpy ligand with metal coordination to one pyridyl and one azo function and one nonbonding Re-N interaction at 3.293 {\AA} to the 2nd pyridyl N atom. The dinuclear 2 with two azoimine-coordinated metal centers is distinguished by the trans arrangement of the chloride ligands with respect to the Re2(\textgreek{m}-abpy) plane, the Re-Re distance is 5.033(7) {\AA}. The azo bond lengths at 1.272(9) (1) and 1.304(10) A (2) indicate substantial \textgreek{p} back donation from the Re(I) centers into the \textgreek{p}*(abpy) orbital. Spectroelectrochem. reveals the successive occupation of the \textgreek{p}*(abpy) orbital by electrons; metal-to-ligand charge transfer features are shifted to higher energies and carbonyl stretching bands to lower wavenumbers. The EPR spectra of both radical anion intermediates 1$\surd$- and 2$\surd$- are dominated by very similar 185,187Re hyperfine splitting, ruling out a mixed-valent formulation. The 2nd electron uptake is followed by the rapid loss of one chloride, leading to an unsym. species in the dinuclear system. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Hartmann, H. and Scheiring, T. and Fiedler, J. and Kaim, W.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/29bcccb248a39ffb9e7402d37abf0aff5/huebleriac},
doi = {10.1016/S0022-328X(00)00282-5},
interhash = {328b2b4502fa6063781f0b0473a640b7},
intrahash = {9bcccb248a39ffb9e7402d37abf0aff5},
journal = {Journal of Organometallic Chemistry},
keywords = {azobispyridine carbonyl chloro chloro;electrochem chloro;rhenium crystal prepn redn rhenium spectroelectrochem structure},
number = 2,
pages = {267--272},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Structures and spectroelectrochemistry (UV-vis, IR, EPR) of complexes [(OC)3ClRe]n(abpy), n = 1, 2; abpy = 2,2'-azobispyridine},
volume = 604,
year = 2000
}