Redukce kov vs. ligand v komplexech dipyridol[3,2-a:2 '', 3''-c]phenazinu a příbuzných ligandů s [(C5Me5)CIM ] +, M = Rh nebo Ir: Důkaz vlivu spíše potenciálu než orbitalu na redukční štěpení vazby kov-chlorid

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F04%3A00101045" target="_blank" >RIV/61388955:_____/04:00101045 - isvavai.cz</a>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Metal vs. Ligand Reduction in Complexes of Dipyridol[3,2-a:2'', 3''-c]phenayine and Related Ligands with [(C5Me5)CIM]+, M = Rh or Ir: Evidence for Potential Rather Than Orbital Control in the Reductive Cleavage of the Metal-Chloride Bond

Popis výsledku v původním jazyce

Complexes between the chlorometal(III) cations [(C5Me5)ClM]+, M = Rh or Ir, and the 1,10-phenanthroline-derived .alpha.-diimine (NN) ligands dipyrido[3,2-a;2'',3''-c]phenazine (dppz), 1,4,7,10-tetraazaphenanthrene (tap), or 1,10-phenanthroline-5,6-dione(pdo) were investigated by cyclic voltammetry, EPR and UV-Vis-NIR spectroelectrochemistry with respect to either ligand-based or metal-centered (and then chloride-dissociative) reduction. Two low-lying unoccupied MOs are present in each of these three NNligands, however, their different energies and interface properties are responsible for different results. Metal-centered chloride-releasing reduction was observed for complexes of the DNA-intercalation ligands dppz and tap to yield compounds [(NN)(C5Me5)M] in a two electron step. The separation of .alpha.-diimine centered optical orbitals and phenazine-based redox orbitals is apparent from the EPR and UV-Vis-NIR spectroelectrochemistry of [(dppz)(C5Me5)M]o/.-/2-.

Název v anglickém jazyce

Metal vs. Ligand Reduction in Complexes of Dipyridol[3,2-a:2'', 3''-c]phenayine and Related Ligands with [(C5Me5)CIM]+, M = Rh or Ir: Evidence for Potential Rather Than Orbital Control in the Reductive Cleavage of the Metal-Chloride Bond

Popis výsledku anglicky

Complexes between the chlorometal(III) cations [(C5Me5)ClM]+, M = Rh or Ir, and the 1,10-phenanthroline-derived .alpha.-diimine (NN) ligands dipyrido[3,2-a;2'',3''-c]phenazine (dppz), 1,4,7,10-tetraazaphenanthrene (tap), or 1,10-phenanthroline-5,6-dione(pdo) were investigated by cyclic voltammetry, EPR and UV-Vis-NIR spectroelectrochemistry with respect to either ligand-based or metal-centered (and then chloride-dissociative) reduction. Two low-lying unoccupied MOs are present in each of these three NNligands, however, their different energies and interface properties are responsible for different results. Metal-centered chloride-releasing reduction was observed for complexes of the DNA-intercalation ligands dppz and tap to yield compounds [(NN)(C5Me5)M] in a two electron step. The separation of .alpha.-diimine centered optical orbitals and phenazine-based redox orbitals is apparent from the EPR and UV-Vis-NIR spectroelectrochemistry of [(dppz)(C5Me5)M]o/.-/2-.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CG - Elektrochemie

OECD FORD obor

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Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2004

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

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Svazek periodika

43

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

1530-1538

Kód UT WoS článku

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EID výsledku v databázi Scopus

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