The conjugative bridging of organometallic reaction centers in heterodinuclear complexes (OC)3ClRe(m-L)MCl(C5Me5)+, M = Rh or Ir - Spectroscopic consequences of reductive activation
Heterobimetallic rhenium-rhodium and rhenium-iridium organometallic complexes bridged by conjugated bis-chelate nitrogen heterocyclic ligands, were prepd.; their electroredn. gives corresponding radical-anions, which were studied by ESR and IR spectroscopy. Complexes (I-III) as PF6- salts; M = (h5-C5Me5)RhCl, (h5-C5Me5)IrCl were prepd. by complexation of corresponding rhenium complexes Re(CO)3Cl(bpip), Re(CO)3Cl(bptz) and Re(CO)3Cl(bpym) (bpip, bptz, bpym are for 2,5-bis(1-phenyliminoethyl)pyrazine, 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine and 2,2'-bipyrimidine, resp.) with (h5-C5Me5)MCl2. The stepwise reductive activation accompanied by chloride dissocn. was studied by cyclic voltammetry and spectroelectrochem. in the range of CO stretching vibrations (IR), charge transfer absorptions (UV/Vis) and ESR for paramagnetic intermediates of the mono- and heterobinuclear compds. While complexes of bpip and bptz form one-electron reduced radical intermediates (OC)3ClRe(m-L)MCl(C5Me5).bul., the compds. with bpym follow MCl-dissociative two-electron redn. pathway, giving (OC)3ClRe(m-L)M(C5Me5). on SciFinder(R)
%0 Journal Article
%1 Kaim.2004
%A Kaim, Wolfgang
%A Scheiring, Thomas
%A Weber, Michael
%A Fiedler, Jan.
%D 2004
%J Zeitschrift fuer Anorganische und Allgemeine Chemie
%K ESR IR UV arom bis bridged chelate chelate;redox chelate;rhenium compd complex complex;spectroelectrochem conjugated electrochem half heterobinuclear heterocyclic iridium ligand;rhodium nitrogen potential prepn;pyrazine prepn;redn pyrimidine rhenium rhodium sandwich tetrazole
%N 12
%P 1883--1893
%R 10.1002/zaac.200400174
%T The conjugative bridging of organometallic reaction centers in heterodinuclear complexes (OC)3ClRe(m-L)MCl(C5Me5)+, M = Rh or Ir - Spectroscopic consequences of reductive activation
%V 630
%X Heterobimetallic rhenium-rhodium and rhenium-iridium organometallic complexes bridged by conjugated bis-chelate nitrogen heterocyclic ligands, were prepd.; their electroredn. gives corresponding radical-anions, which were studied by ESR and IR spectroscopy. Complexes (I-III) as PF6- salts; M = (h5-C5Me5)RhCl, (h5-C5Me5)IrCl were prepd. by complexation of corresponding rhenium complexes Re(CO)3Cl(bpip), Re(CO)3Cl(bptz) and Re(CO)3Cl(bpym) (bpip, bptz, bpym are for 2,5-bis(1-phenyliminoethyl)pyrazine, 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine and 2,2'-bipyrimidine, resp.) with (h5-C5Me5)MCl2. The stepwise reductive activation accompanied by chloride dissocn. was studied by cyclic voltammetry and spectroelectrochem. in the range of CO stretching vibrations (IR), charge transfer absorptions (UV/Vis) and ESR for paramagnetic intermediates of the mono- and heterobinuclear compds. While complexes of bpip and bptz form one-electron reduced radical intermediates (OC)3ClRe(m-L)MCl(C5Me5).bul., the compds. with bpym follow MCl-dissociative two-electron redn. pathway, giving (OC)3ClRe(m-L)M(C5Me5). on SciFinder(R)
@article{Kaim.2004,
abstract = {Heterobimetallic rhenium-rhodium and rhenium-iridium organometallic complexes bridged by conjugated bis-chelate nitrogen heterocyclic ligands, were prepd.; their electroredn. gives corresponding radical-anions, which were studied by ESR and IR spectroscopy. Complexes (I-III) [as PF6- salts; M = (\textgreek{h}5-C5Me5)RhCl, (\textgreek{h}5-C5Me5)IrCl] were prepd. by complexation of corresponding rhenium complexes Re(CO)3Cl(bpip), Re(CO)3Cl(bptz) and Re(CO)3Cl(bpym) (bpip, bptz, bpym are for 2,5-bis(1-phenyliminoethyl)pyrazine, 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine and 2,2'-bipyrimidine, resp.) with [(\textgreek{h}5-C5Me5)MCl]2. The stepwise reductive activation accompanied by chloride dissocn. was studied by cyclic voltammetry and spectroelectrochem. in the range of CO stretching vibrations (IR), charge transfer absorptions (UV/Vis) and ESR for paramagnetic intermediates of the mono- and heterobinuclear compds. While complexes of bpip and bptz form one-electron reduced radical intermediates [(OC)3ClRe(\textgreek{m}-L)MCl(C5Me5)].bul., the compds. with bpym follow MCl-dissociative two-electron redn. pathway, giving [(OC)3ClRe(\textgreek{m}-L)M(C5Me5)]. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Kaim, Wolfgang and Scheiring, Thomas and Weber, Michael and Fiedler, Jan.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2fd5463166a06bf4a5f23cc0750009b79/b_schwederski},
doi = {10.1002/zaac.200400174},
interhash = {92aa14ea83b3c7ab8303e2b1f266d0c1},
intrahash = {fd5463166a06bf4a5f23cc0750009b79},
issn = {0044-2313},
journal = {Zeitschrift fuer Anorganische und Allgemeine Chemie},
keywords = {ESR IR UV arom bis bridged chelate chelate;redox chelate;rhenium compd complex complex;spectroelectrochem conjugated electrochem half heterobinuclear heterocyclic iridium ligand;rhodium nitrogen potential prepn;pyrazine prepn;redn pyrimidine rhenium rhodium sandwich tetrazole},
number = 12,
pages = {1883--1893},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {The conjugative bridging of organometallic reaction centers in heterodinuclear complexes [(OC)3ClRe(\textgreek{m}-L)MCl(C5Me5)]+, M = Rh or Ir - Spectroscopic consequences of reductive activation},
volume = 630,
year = 2004
}