Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I)

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F14%3A00434726" target="_blank" >RIV/61388955:_____/14:00434726 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/om500039a" target="_blank" >http://dx.doi.org/10.1021/om500039a</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/om500039a" target="_blank" >10.1021/om500039a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I)

Popis výsledku v původním jazyce

The complex cations [Cu(dippf)(DML)](+) ([1](+)) and [Cu(dppf)(DML)](+) ([2](+)), where dippf = 1,1'-bis(diisopropylphosphino)ferrocene, dppf = 1,1'-bis(diphenylphosphino)ferrocene, and DML = 1,3-dimethyllumazine, were prepared and crystallized as BF4- or PF6- salts. Structure determinations of the tetrafluoroborates revealed asymmetric O-4,N-5 chelation of DML to copper(I) with longer Cu-O bonds of about 2.25 angstrom. Reversible oxidation to [1](2+) and [2](2+) proceeds at the ferrocene units, while reduction leads to the neutral radical complexes [1] and [2] with the unpaired electron localized on the DML ligand. The occurrence of two voltammetric steps for the one-electron-reduction process is attributed to a two-species equilibrium caused by the hemilabile coordination of DML. Electrochemical and spectroelectrochemical measurements (UV-vis, IR) reveal increased coordination lability of the reduced complexes and their slow fragmentation.

Název v anglickém jazyce

Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I)

Popis výsledku anglicky

The complex cations [Cu(dippf)(DML)](+) ([1](+)) and [Cu(dppf)(DML)](+) ([2](+)), where dippf = 1,1'-bis(diisopropylphosphino)ferrocene, dppf = 1,1'-bis(diphenylphosphino)ferrocene, and DML = 1,3-dimethyllumazine, were prepared and crystallized as BF4- or PF6- salts. Structure determinations of the tetrafluoroborates revealed asymmetric O-4,N-5 chelation of DML to copper(I) with longer Cu-O bonds of about 2.25 angstrom. Reversible oxidation to [1](2+) and [2](2+) proceeds at the ferrocene units, while reduction leads to the neutral radical complexes [1] and [2] with the unpaired electron localized on the DML ligand. The occurrence of two voltammetric steps for the one-electron-reduction process is attributed to a two-species equilibrium caused by the hemilabile coordination of DML. Electrochemical and spectroelectrochemical measurements (UV-vis, IR) reveal increased coordination lability of the reduced complexes and their slow fragmentation.

Druh

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

CEP obor

CG - Elektrochemie

OECD FORD obor

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Projekt

<a href="/cs/project/LD14129" target="_blank" >LD14129: Struktura a dynamika excitovaných a redoxních stavů fotokatalytických komplexů</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2014

Kód důvěrnosti údajů

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

Název periodika

Organometallics

ISSN

0276-7333

e-ISSN

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Svazek periodika

33

Číslo periodika v rámci svazku

18

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

4784-4791

Kód UT WoS článku

000342180800026

EID výsledku v databázi Scopus

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