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Description
  • Reakce {(.mu.-bpym)[RuCl(terpy)]2}(PF6)2, bpym= 2,2´-bipyrimidine a terpy = 2,2´:6´,2´´-terpyridin, s NaNO2 poskytuje{(.mu.-bpym)[Ru(NO2)(terpy)]2}(PF6)2. Oba dvojjaderné komplexy mohou podstoupit dva reversibilní bpym-centralizované jednoelektronové redukční procesy a dva jednoelektronové oxidační kroky centralizované na kovu, přičemž oxidace probíhá přes meziprodukt se smíšenou valencí a slabým intermetalickým propojením. Okyselení {(.mu.-bpym)[Ru(NO2)(terpy)]2}(PF6)2 nevede k očekávanému {(.mu.-bpym)[Ru(NO)(terpy)]2}6+ ale, pravděpodobně kvůli vysokému náboji, k nerozpusnému, ale strukturálně a IR-spektroskopicky charakterizovanému pseudo-basickému produktu syn-{(.mu.-bpym-(4-OH))[Ru(NO)(terpy)]2}(PF6)5. Přidání jednoho hydroxidu k jedné ze 4-pozic bis-chelátového bpym přeruší aromatickou .pi. konjugaci a je doprovázeno odpovídající změnou intra-pyrimidinových vazebných délek. (cs)
  • Reaction of {(.mu.-bpym)[RuCl(terpy)]2}(PF6)2, bpym= 2,2´-bipyrimidine and terpy = 2,2´:6´,2´´-terpyridine, with NaNO2 yields{(.mu.-bpym)[Ru(NO2)(terpy)]2}(PF6)2. Both dinuclear complexes can undergo two reversible bpym-centered one-electron reduction processes and two metal-centered one-electron oxidation steps, the latter involving mixed-valent intermediates with weak intermetallic coupling. Acidification of {(.mu.-bpym)[Ru(NO2)(terpy)]2}(PF6)2 does not lead to the expected {(.mu.-bpym)[Ru(NO)(terpy)]2}6+ but, probably because of the high charge, to the insoluble but structurally and IR-spectroscopically characterised pseudo-base product syn-{(.mu.-bpym-(4-OH))[Ru(NO)(terpy)]2}(PF6)5. The addition of one hydroxide to one of the 4-positions of bis-chelating bpym interrupts the aromatic .pi. conjugation and is accompanied by corresponding intra-pyrimidine bond length variations.
  • Reaction of {(.mu.-bpym)[RuCl(terpy)]2}(PF6)2, bpym= 2,2´-bipyrimidine and terpy = 2,2´:6´,2´´-terpyridine, with NaNO2 yields{(.mu.-bpym)[Ru(NO2)(terpy)]2}(PF6)2. Both dinuclear complexes can undergo two reversible bpym-centered one-electron reduction processes and two metal-centered one-electron oxidation steps, the latter involving mixed-valent intermediates with weak intermetallic coupling. Acidification of {(.mu.-bpym)[Ru(NO2)(terpy)]2}(PF6)2 does not lead to the expected {(.mu.-bpym)[Ru(NO)(terpy)]2}6+ but, probably because of the high charge, to the insoluble but structurally and IR-spectroscopically characterised pseudo-base product syn-{(.mu.-bpym-(4-OH))[Ru(NO)(terpy)]2}(PF6)5. The addition of one hydroxide to one of the 4-positions of bis-chelating bpym interrupts the aromatic .pi. conjugation and is accompanied by corresponding intra-pyrimidine bond length variations. (en)
Title
  • Pseudo-base formation in the attempted synthesis of a conjugatively coupled bis(nitrosylruthenium) complex and spectroelectrochemistry of bipyrimidine-bridged dinuclear Ru(terpy)X precursor compounds (X = Cl, NO2)
  • Pseudo-base formation in the attempted synthesis of a conjugatively coupled bis(nitrosylruthenium) complex and spectroelectrochemistry of bipyrimidine-bridged dinuclear Ru(terpy)X precursor compounds (X = Cl, NO2) (en)
  • Tvorba pseudo-báze v pokusu o syntézu konjugačně propojeného bis-nitrosylrutheniového komplexu a spektroelektrochemie dvojjaderných prekurzorových sloučenin, bipyrimidinovým můstkem spojených Ru(terpy)X (X = Cl, NO2) (cs)
skos:prefLabel
  • Pseudo-base formation in the attempted synthesis of a conjugatively coupled bis(nitrosylruthenium) complex and spectroelectrochemistry of bipyrimidine-bridged dinuclear Ru(terpy)X precursor compounds (X = Cl, NO2)
  • Pseudo-base formation in the attempted synthesis of a conjugatively coupled bis(nitrosylruthenium) complex and spectroelectrochemistry of bipyrimidine-bridged dinuclear Ru(terpy)X precursor compounds (X = Cl, NO2) (en)
  • Tvorba pseudo-báze v pokusu o syntézu konjugačně propojeného bis-nitrosylrutheniového komplexu a spektroelektrochemie dvojjaderných prekurzorových sloučenin, bipyrimidinovým můstkem spojených Ru(terpy)X (X = Cl, NO2) (cs)
skos:notation
  • RIV/61388955:_____/08:00309644!RIV09-AV0-61388955
http://linked.open...avai/riv/aktivita
http://linked.open...avai/riv/aktivity
  • P(IAA400400505), P(LC510), Z(AV0Z40400503)
http://linked.open...iv/cisloPeriodika
  • 7
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
  • 390939
http://linked.open...ai/riv/idVysledku
  • RIV/61388955:_____/08:00309644
http://linked.open...riv/jazykVysledku
http://linked.open.../riv/klicovaSlova
  • Creutz-Taube ion; electron transfer; redox system; center-dot (en)
http://linked.open.../riv/klicoveSlovo
http://linked.open...odStatuVydavatele
  • GB - Spojené království Velké Británie a Severního Irska
http://linked.open...ontrolniKodProRIV
  • [A60FF7A622D7]
http://linked.open...i/riv/nazevZdroje
  • Dalton Transactions
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
  • -
http://linked.open...iv/tvurceVysledku
  • Fiedler, Jan
  • Kaim, W.
  • Sieger, M.
  • Su, Ch. Y.
  • Singh, P.
http://linked.open...ain/vavai/riv/wos
  • 000252979000004
http://linked.open...n/vavai/riv/zamer
issn
  • 1477-9226
number of pages
is http://linked.open...avai/riv/vysledek of
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