Pregled bibliografske jedinice broj: 644401
Dicyclopalladated Complexes of Asymmetrically Substituted Azobenzenes: Synthesis, Kinetics and Mechanisms
Dicyclopalladated Complexes of Asymmetrically Substituted Azobenzenes: Synthesis, Kinetics and Mechanisms // Inorganic chemistry, 52 (2013), 21; 12749-12757 doi:10.1021/ic402017v (međunarodna recenzija, članak, znanstveni)
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Naslov
Dicyclopalladated Complexes of Asymmetrically Substituted Azobenzenes: Synthesis, Kinetics and Mechanisms
Autori
Juribašić, Marina ; Budimir, Ana ; Kazazić, Snježana ; Ćurić, Manda
Izvornik
Inorganic chemistry (0020-1669) 52
(2013), 21;
12749-12757
Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni
Ključne riječi
azobenzenes; dicyclopalladation; kinetics; mechanism; DFT
Sažetak
Two series of new dicyclopalladated complexes {; ; ; (DMF)PdCl(mu-R1C6H3N=NC6H3R2)PdCl(DMF)}; ; ; of 4, 4’-functionalized azobenzenes with substituents of varying electron-donating or electron-withdrawing strength (R1=H, NMe2 ; R2=H, Cl, Br, I, OMe, PhNH, CO2H, SO3Na, NO2) have been synthesized and fully characterized. 1H NMR spectroscopy along with the ESI mass spectrometry unambiguously identified the new complexes in the solution and their solid-state structures were determined by X-ray crystallography. The presence of easily exchangeable solvent ligands was confirmed by 1H NMR spectroscopy, X-ray experiments and ESI mass spectrometry. The complexes were additionally characterized by UV-vis and fluorescence spectroscopies. The effect of different 4, 4’-substituents on the formation rate of mono- and dicyclopalladated azobenzenes was studied by the UV-vis spectroscopy. The experimental results are complemented by the quantum-chemical (DFT) calculations in order to rationalize the kinetic results as well as substituent effects on the reaction rates. It was found that the mono- and dicyclopalladation reactions of azobenzenes proceed in two consecutive processes, adduct formation and palladation step. The rate-determining step in both palladations is the breaking of the ortho C–H bond that has been confirmed as an electrophilic substitution process by Hammett correlations and DFT calculations.
Izvorni jezik
Engleski
Znanstvena područja
Kemija
POVEZANOST RADA
Projekti:
006-0061247-0009 - Kinetika i mehanizam katalitičkog antioksidacijskog djelovanja Mn-porfirina (Budimir, Ana, MZOS ) ( CroRIS)
098-0982915-2945 - Spektroskopija, kemijska svojstva i reakcije biološki aktivnih molekula (Kovač, Branka, MZOS ) ( CroRIS)
098-0982915-2950 - Dizajn, sinteza i svojstva organskih liganada i njihovih metalnih kompleksa (Ćurić, Manda, MZOS ) ( CroRIS)
Ustanove:
Farmaceutsko-biokemijski fakultet, Zagreb,
Institut "Ruđer Bošković", Zagreb
Profili:
Marina Juribašić Kulcsar
(autor)
Snježana Kazazić
(autor)
Manda Ćurić
(autor)
Ana Budimir
(autor)
Citiraj ovu publikaciju:
Časopis indeksira:
- Current Contents Connect (CCC)
- Web of Science Core Collection (WoSCC)
- Science Citation Index Expanded (SCI-EXP)
- SCI-EXP, SSCI i/ili A&HCI
- Scopus
- MEDLINE