%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)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(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 }