Naslov
Kinetics and mechanism of the C-H bond activation in azobenzenes and their monopalladated derivatives by PdII

Autori
Budimir, Ana ; Barišić, Dajana ; Bjelopetrović, Alen ; Babić, Darko ; Ćurić, Manda

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
Adriatic NMR conference 2021 : book of abstracts / Bregović, Nikola ; Namjesnik, Danijel ; Novak, Predrag ; Parlov Vuković, Jelena - Zagreb : Hrvatsko kemijsko društvo, 2021, 27-27

Skup
The Adriatic NMR Conference 2021

Mjesto i datum
Primošten, Hrvatska, 13.09.2021. - 15.09.2021

Vrsta sudjelovanja
Pozvano predavanje

Vrsta recenzije
Podatak o recenziji nije dostupan

Ključne riječi
kinetics ; azobenzene ; palladium ; C-H bond activation

Sažetak
Cyclopalladation is one of the best known Pd-C bond formation reactions to generate the palladacycles. Palladacycles have been identified as crucial intermediates in many organic reactions promoted by palladium precursors leading to functionalized hydrocarbons. Therefore, a detailed understanding of the cyclopalladation pathways of various organic substrates is essential. This presentation describes a comprehensive kinetico- mechanistic study of cyclopalladation reactions involving the activation of azobenzene C–H bonds by cis- [PdCl2(DMF)2] in DMF, both for the free ligands and for their already monopalladated derivatives. All reactions were monitored by time- resolved NMR and UV-Vis spectroscopy at different Pd-precursor concentrations, temperatures and pressures. The results suggest the operation of an electrophilic substitution intimate mechanism for both the mono- and dipalladation reactions, occurring from the coordination compound and the monopalladated intermediates, respectively. The process involves a deprotonation of the C–H bond, which is aided by the presence of a coordinated DMF molecule acting as a base. The obtained results represent an important contribution with a remarkable synergy between diverse but complementary techniques. This complete picture of the whole process will allow the better design and preparation of new cyclopalladated complexes in the Pd-catalyzed reactions of substrates having multiple C–H bonds available for functionalization.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA