About: Mixed-valent and radical states of complexes [(bpy)(2)M(.mu.-abpy)M´(bpy)(2)](n+), M,M´ = Ru or Os, abpy=2,2´-azobispyridine: Electron transfer vs. hole transfer mechanism in azo ligand-bridged complexes     Goto   Sponge   NotDistinct   Permalink

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  • The title complexes were obtained as MIIM´II species. One-electron reduction produces radical complexes [(bpy)2M(.mu.-abpy)M´(bpy)2].3+ and [(bpy)2M(abpy)].+ with significant contributions from the metals, as evident from the EPR effects on successive replacement of ruthenium by osmium with its much higher spin-orbit coupling constant. Further reduction was monitored by UV/Vis spectroelectrochemistry. Oxidation produced OsIII EPR signals for [(bpy)2Os(abpy)]3+ and [(bpy)2Os(.mu.-abpy)Ru(bpy)2]5+, indicating a RuIIOsIII species for the latter. The much higher comproportionation constant Kc for the mixed valent diosmium(III,II) state (Kc > 1015) in comparison to the diruthenium(III,II) analogue with Kc = 1010 confirms the electron transfer alternative for the valence exchange mechanism, in contrast to the hole transfer established for analogous dinuclear complexes with the formally related diacylhydrazido(2-) bridging ligands.
  • The title complexes were obtained as MIIM´II species. One-electron reduction produces radical complexes [(bpy)2M(.mu.-abpy)M´(bpy)2].3+ and [(bpy)2M(abpy)].+ with significant contributions from the metals, as evident from the EPR effects on successive replacement of ruthenium by osmium with its much higher spin-orbit coupling constant. Further reduction was monitored by UV/Vis spectroelectrochemistry. Oxidation produced OsIII EPR signals for [(bpy)2Os(abpy)]3+ and [(bpy)2Os(.mu.-abpy)Ru(bpy)2]5+, indicating a RuIIOsIII species for the latter. The much higher comproportionation constant Kc for the mixed valent diosmium(III,II) state (Kc > 1015) in comparison to the diruthenium(III,II) analogue with Kc = 1010 confirms the electron transfer alternative for the valence exchange mechanism, in contrast to the hole transfer established for analogous dinuclear complexes with the formally related diacylhydrazido(2-) bridging ligands. (en)
  • Titulní komplexy byly získány jako MIIM'II částice. Jednoelektronová redukce poskytuje radikálové komplexy [(bpy)2M(.mu.-abpy)M´(bpy)2].3+ a [(bpy)2M(abpy)].+ s významnými příspěvky od kovů, jak je evidentní z EPR odezvy na postupné nahrazení ruthenia osmiem s mnohem vyšší konstantou spin-orbitálního spojení. Další redukce byla sledována pomocí UV/VIS spektroelektrochemie. Oxidace poskytla OsIII EPR signály pro [(bpy)2Os(abpy )]3+ a [(bpy)2Os(.mu.-abpy)Ru(bpy)2]5+, ukazující na RuIIOsIII typ u druhé sloučeniny. Mnohem vyšší komproporcionační konstanta Kc pro diosmium(III,II) stav se smíšenou valencí (Kc > 1015) ve srovnání k diruthenium(III,II) analogem s Kc = 1010 potvrzuje alternativu elektronového přenosu pro mechanismus výměny valence, na rozdíl od děrového přenosu fungujícího u podobných dvojjaderných komplexů s formálně příbuznými diacylhydrazido(2-) můstkovými ligandy. (cs)
Title
  • Mixed-valent and radical states of complexes [(bpy)(2)M(.mu.-abpy)M´(bpy)(2)](n+), M,M´ = Ru or Os, abpy=2,2´-azobispyridine: Electron transfer vs. hole transfer mechanism in azo ligand-bridged complexes
  • Mixed-valent and radical states of complexes [(bpy)(2)M(.mu.-abpy)M´(bpy)(2)](n+), M,M´ = Ru or Os, abpy=2,2´-azobispyridine: Electron transfer vs. hole transfer mechanism in azo ligand-bridged complexes (en)
  • Stavy se smíšenou valencí a radikálové stavy komplexů [(bpy)2M(.mu.-abpy)M´(bpy)2]n+, M,M´ = Ru nebo Os, abpy = 2,2´-Azobispyridin: Elektronový přenos versus děrový přenosový mechanismus v kompexech s můstkovým azo ligandem (cs)
skos:prefLabel
  • Mixed-valent and radical states of complexes [(bpy)(2)M(.mu.-abpy)M´(bpy)(2)](n+), M,M´ = Ru or Os, abpy=2,2´-azobispyridine: Electron transfer vs. hole transfer mechanism in azo ligand-bridged complexes
  • Mixed-valent and radical states of complexes [(bpy)(2)M(.mu.-abpy)M´(bpy)(2)](n+), M,M´ = Ru or Os, abpy=2,2´-azobispyridine: Electron transfer vs. hole transfer mechanism in azo ligand-bridged complexes (en)
  • Stavy se smíšenou valencí a radikálové stavy komplexů [(bpy)2M(.mu.-abpy)M´(bpy)2]n+, M,M´ = Ru nebo Os, abpy = 2,2´-Azobispyridin: Elektronový přenos versus děrový přenosový mechanismus v kompexech s můstkovým azo ligandem (cs)
skos:notation
  • RIV/61388955:_____/06:00040874!RIV07-AV0-61388955
http://linked.open.../vavai/riv/strany
  • 821;829
http://linked.open...avai/riv/aktivita
http://linked.open...avai/riv/aktivity
  • P(GA203/03/0821), P(IAA400400505), P(LC510), Z(AV0Z40400503)
http://linked.open...iv/cisloPeriodika
  • 3
http://linked.open...vai/riv/dodaniDat
http://linked.open...aciTvurceVysledku
http://linked.open.../riv/druhVysledku
http://linked.open...iv/duvernostUdaju
http://linked.open...titaPredkladatele
http://linked.open...dnocenehoVysledku
  • 485984
http://linked.open...ai/riv/idVysledku
  • RIV/61388955:_____/06:00040874
http://linked.open...riv/jazykVysledku
http://linked.open.../riv/klicovaSlova
  • mixed valency; osmium compounds; radical ligands; ruthenium compounds; spectroslectrochemistry (en)
http://linked.open.../riv/klicoveSlovo
http://linked.open...odStatuVydavatele
  • NL - Nizozemsko
http://linked.open...ontrolniKodProRIV
  • [98E144C6D8AA]
http://linked.open...i/riv/nazevZdroje
  • Inorganica chimica acta
http://linked.open...in/vavai/riv/obor
http://linked.open...ichTvurcuVysledku
http://linked.open...cetTvurcuVysledku
http://linked.open...vavai/riv/projekt
http://linked.open...UplatneniVysledku
http://linked.open...v/svazekPeriodika
  • 359
http://linked.open...iv/tvurceVysledku
  • Fiedler, Jan
  • Kaim, W.
  • Heilmann, M.
  • Duboc, C.
  • Frantz, S.
http://linked.open...n/vavai/riv/zamer
issn
  • 0020-1693
number of pages
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