Stabilizing the Elusive ortho-Quinone/Copper(I) Oxidation State Combination through .pi./.pi. Interaction in an Isolated Complex
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F08%3A00317768" target="_blank" >RIV/61388955:_____/08:00317768 - isvavai.cz</a>
Result on the web
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DOI - Digital Object Identifier
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Alternative languages
Result language
angličtina
Original language name
Stabilizing the Elusive ortho-Quinone/Copper(I) Oxidation State Combination through .pi./.pi. Interaction in an Isolated Complex
Original language description
The heterodinuclear compound [(PhenQ)Cu(dppf)](BF4), PhenQ = 9,10-phenanthrenequinone and dppf = 1,1´-bis(diphenylphosphino)ferrocene, was identified structurally and spectroscopically (NMR, IR, UV-vis) as a copper(I) complex of a completely unreduced ortho-quinone. Crystallographic and DFT calculation results suggest that this stabilization of a hitherto elusive arrangement is partially owed to intramolecular .pi./.pi. interactions phenyl/PhenQ. Intermolecular PhenQ/PhenQ .pi. stacking is also observedin the crystal. According to DFT calculations, the .pi. interactions are responsible for the considerably distorted coordination geometry at CuI with one short and one longer Cu-O and Cu-P bond, respectively, and with bond angles at copper ranging from99 o to 133o. Electrochemical reduction proceeds reversibly at low temperatures to yield an EPR spectroscopically characterized semiquinone-copper(I) species.
Czech name
Stabilizace neobvyklé kombinace oxidačního stavu v ortho-chinon/Cu(I) .pi./.pi. interakcí v izolovaném komplexu
Czech description
Heteronukleární komplex [(PhenQ)Cu(dppf)](BF4), PhenQ = 9,10-phenanthrenequinon a dppf = 1,1?-bis(diphenylphosphino)ferrocene, byl identifikován strukturně a spektroscopicky (NMR, IR, UV-Vis) jako Cu(I) komplex kompletně neredukovaného ortho-chinonu. Strukturní měření a výsledky DFT výpočtů objasňují, že stabilizace doposud nepozorovaného uspořádání je částečně způsobeno intramolekulární .pi./.pi. interakcí phenyl/PhenQ.
Classification
Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CG - Electrochemistry
OECD FORD branch
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Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)
Others
Publication year
2008
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of the American Chemical Society
ISSN
0002-7863
e-ISSN
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Volume of the periodical
130
Issue of the periodical within the volume
46
Country of publishing house
US - UNITED STATES
Number of pages
2
Pages from-to
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UT code for WoS article
000263311300005
EID of the result in the Scopus database
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