Measured and Calculated Oxidation Potentials of 1-X-12-Y-CB11Me10- Anions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F12%3A00378973" target="_blank" >RIV/61388963:_____/12:00378973 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/12:00378973

Výsledek na webu

<a href="http://dx.doi.org/10.1021/ic2026939" target="_blank" >http://dx.doi.org/10.1021/ic2026939</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/ic2026939" target="_blank" >10.1021/ic2026939</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Measured and Calculated Oxidation Potentials of 1-X-12-Y-CB11Me10- Anions

Popis výsledku v původním jazyce

Cyclic voltammetry of 31 icosahedral carborane anions 1-X-12-Y-CB11Me10- at a Pt electrode in liquid SO2 revealed a completely reversible one-electron oxidation even at low scan rates, except for the anions with Y = I, which are oxidized irreversibly upto a scan rate of 5.0 V/s, and the anion with X = COOH and Y = H, whose oxidation is irreversible at scan rates below 1.0 V/s. Relative reversible oxidation potentials agree well with RI-B3LYP/TZVPP,COSMO and significantly less well with RI-BP86/TZVPP,COSMO or RI-HF/TZVPP,COSMO calculated adiabatic electron detachment energies. Correlations with HOMO energies of the anions are nearly as good, even though the oxidized forms are subject to considerable Jahn-Teller distortion. Except for the anion with X =F and Y = Me, the oxidation potentials vary linearly with substituent sigma(P) Hammett constants. The slopes (reaction constants) are similar to 0.31 and similar to 0.55 V for positions 1 and 12, respectively.

Název v anglickém jazyce

Measured and Calculated Oxidation Potentials of 1-X-12-Y-CB11Me10- Anions

Popis výsledku anglicky

Cyclic voltammetry of 31 icosahedral carborane anions 1-X-12-Y-CB11Me10- at a Pt electrode in liquid SO2 revealed a completely reversible one-electron oxidation even at low scan rates, except for the anions with Y = I, which are oxidized irreversibly upto a scan rate of 5.0 V/s, and the anion with X = COOH and Y = H, whose oxidation is irreversible at scan rates below 1.0 V/s. Relative reversible oxidation potentials agree well with RI-B3LYP/TZVPP,COSMO and significantly less well with RI-BP86/TZVPP,COSMO or RI-HF/TZVPP,COSMO calculated adiabatic electron detachment energies. Correlations with HOMO energies of the anions are nearly as good, even though the oxidized forms are subject to considerable Jahn-Teller distortion. Except for the anion with X =F and Y = Me, the oxidation potentials vary linearly with substituent sigma(P) Hammett constants. The slopes (reaction constants) are similar to 0.31 and similar to 0.55 V for positions 1 and 12, respectively.

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

2012

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

51

Číslo periodika v rámci svazku

9

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

5128-5137

Kód UT WoS článku

000303952900034

EID výsledku v databázi Scopus

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