Electron delocalization in vinyl ruthenium substituted cyclophanes: Assessment of the through-space and the through-bond pathways

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F11%3A00369086" target="_blank" >RIV/61388955:_____/11:00369086 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1016/j.jorganchem.2011.06.028" target="_blank" >http://dx.doi.org/10.1016/j.jorganchem.2011.06.028</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jorganchem.2011.06.028" target="_blank" >10.1016/j.jorganchem.2011.06.028</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electron delocalization in vinyl ruthenium substituted cyclophanes: Assessment of the through-space and the through-bond pathways

Popis výsledku v původním jazyce

Pseudo-para[2.2]paracyclophane- and [2.1]orthocyclophane-bridged diruthenium complexes 2 and 3 with two interlinked electroactive styryl ruthenium moieties have been prepared and investigated. Both complexes undergo two reversible consecutive one-electron oxidation processes which are separated by 270 or 105 mV. Stepwise electrolysis of the neutral complexes to first the mixed-valent radical cations and then the dioxidized dications under IR monitoring reveal incremental shifts of the charge-sensitive Ru(CO) bands and allow for an assignment of their radical cations as moderately or very weakly coupled mixed-valent systems of class II according to Robin and Day. Ground-state delocalization in the mixed-valent forms of these complexes as based on the COband shifts is considerably larger for the "closed" paracyclophane as for the "half-open" orthocyclophane. Experimental findings are backed by the calculated IR band patterns and spin density distributions for radical cations of slightly

Název v anglickém jazyce

Electron delocalization in vinyl ruthenium substituted cyclophanes: Assessment of the through-space and the through-bond pathways

Popis výsledku anglicky

Pseudo-para[2.2]paracyclophane- and [2.1]orthocyclophane-bridged diruthenium complexes 2 and 3 with two interlinked electroactive styryl ruthenium moieties have been prepared and investigated. Both complexes undergo two reversible consecutive one-electron oxidation processes which are separated by 270 or 105 mV. Stepwise electrolysis of the neutral complexes to first the mixed-valent radical cations and then the dioxidized dications under IR monitoring reveal incremental shifts of the charge-sensitive Ru(CO) bands and allow for an assignment of their radical cations as moderately or very weakly coupled mixed-valent systems of class II according to Robin and Day. Ground-state delocalization in the mixed-valent forms of these complexes as based on the COband shifts is considerably larger for the "closed" paracyclophane as for the "half-open" orthocyclophane. Experimental findings are backed by the calculated IR band patterns and spin density distributions for radical cations of slightly

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

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2011

Kód důvěrnosti údajů

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

Název periodika

Journal of Organometallic Chemistry

ISSN

0022-328X

e-ISSN

—

Svazek periodika

696

Číslo periodika v rámci svazku

20

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

12

Strana od-do

3186-3197

Kód UT WoS článku

000293999500010

EID výsledku v databázi Scopus

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