Dietanolaminski paladijum(II)-kompleks kao katalizator Hekove reakcije

Ugljenik-ugljenik i ugljenik-azot kuplovanja katalizovana prelaznim metalima poslednjih decenija postala su važan deo organskih sinteza i, s pravom se može reći, moćno oruđe sintetičke organske hemije. Paladijum-katalizovano arilovanje olefina, poznato kao Hekova reakcija, jedna je od takvih reakcija. Zahvaljujući sve značajnijoj aplikativnoj ulozi paladijum-katalizovanih reakcija, pre svega njihovoj primeni u farmaceutskoj industriji i pri sintezi mnogih biološki aktivnih jedinjenja, 2010. godine dodeljena je Nobelova nagrada za hemiju Ričardu F. Heku, Eičiju Negišiju i Akiri Suzukiju. U okviru ove disertacije ispitana je katalitička uloga trans-dihlorobis(dietanolamin-N)paladijum(II)-kompleksa (1) u Hekovoj reakciji. Dobijeni rezultati su pokazali da se ovaj kompleks ponaša kao prekatalizator. Metodama funkcionala gustine ispitan je mehanizam transformacija kompleksa 1 u katalitički aktivni Pd(0)-kompleks 5. Razmatran je, kako eksperimentalnim tako i računarskim metodama, uticaj slabe i jake baze na tok reakcije. Takođe, upotrebom diskretnog solvatacionog modela ispitan je uticaj rastvarača na reakcioni mehanizam.Carbon-carbon and carbon-nitrogen couplings catalyzed by transition metals, have become important part of organic chemistry. Palladium catalyzed arylation of olefins, known as Heck reaction, has become a powerful tool of synthetic organic chemistry. Owing to the applicative role of palladium catalyzed reactions, above all their relevance in pharmaceutical industry and synthesis of numerous biologically active compounds, the Nobel Prize in chemistry 2010 was awarded jointly to Richard F. Heck, Eigichi Negichi, and Akira Suzuki. The main topic of this dissertation is catalytic role of the transdichlorobis( diethanolamine-N)palladium(II)-complex (1) in Heck reaction. The obtained results showed that this complex acts as precatalyst. The mechanism of preactivation of 1 into the catalytically active Pd(0)-complex 5 was examined using Density Functional Theory (DFT). The influence of strong and weak bases on the reaction was examined using both experimental and theoretical methods. The influence of solvent was examined by employing the discrete solvation model