Green synthesis of organopalladium photosensitizers
| Autor: | Bjelopetrović, Alen |
|---|---|
| Přispěvatelé: | Ćurić, Manda |
| Jazyk: | chorvatština |
| Rok vydání: | 2021 |
| Předmět: |
optical properties
čvrsto stanje aging mechanism mehanizam mehanokemija solid state PRIRODNE ZNANOSTI. Kemija NATURAL SCIENCES. Chemistry paladocikli palladacycles azobenzen organometalni spojevi azobenzeni optička svojstva starenje udc:54(043.3) mechanochemistry Kemija. Kristalografija. Mineralogija azobenzenes Chemistry. Crystallography. Mineralogy |
| Popis: | Razvijanje čišćih, bržih i ekonomski isplativijih preparativnih metoda jedan je od ciljeva zelene kemije. Izvedivost ovog koncepta zelene kemije demonstrirana je na sintezi organopaladijevih spojeva (paladocikla), zbog njihove važnosti u organskoj sintezi i jedinstvenih optičkih svojstava. Većina sintetskih koraka u ovom radu provedena je reakcijama u čvrstom stanju primjenom metoda mehanokemije ili starenja. Paladocikli s jednom ili dvije veze metal–ugljik i metal–donor dobiveni su aktivacijom veze(a) C–H u azobenzenima različitim katalizatorima paladija(II), a izmjena njihovih anionskih ili neutralnih liganada rezultirala je derivatima s drugačijom reaktivnošću i optičkim svojstvima. Opisane reakcije praćene su spektroskopskim metodama in situ i ex situ što je omogućilo karakterizaciju vrsta uključenih u reakcije, izravan uvid u dinamiku i reakcijske putove, te faktore koji kontroliraju reaktivnost i selektivnost, kao i optimizaciju procesa mljevenja. Primjena razvijenih metoda i koncepata omogućit će sintezu novih organopaladijevih spojeva na ekološki prihvatljiv način, izravnu i selektivnu zamjenu veze C–H drugim funkcionalnim skupinama, te razvoj novih katalizatora. The development of clean, fast, and cost-effective preparative methods is one of the objectives of green chemistry. The feasibility of the green chemistry concept is demonstrated on the synthesis of organopalladium compounds (palladacycles), important due to their wide application in organic synthesis and unique optical properties. The majority of synthetic steps in this thesis were performed by solid-state synthetic method, mechanochemistry and aging. Palladacycles with one or two metal-carbon and metal-donor bonds were prepared via C–H bond(s) activation in azobenzenes by various Pd(II) catalysts, and the exchange of their anionic or neutral ligands resulted in derivatives with different reactivity and optical properties. The described reactions were monitored in situ and ex situ by spectroscopic methods, which enabled the characterization of the species involved in the reactions, direct insight into the reaction pathways, insight into the factors controlling reactivity and selectivity, and optimization of the grinding process. The application of the developed methods and concepts will enable synthesis of new organopalladium compounds, direct and selective replacement of the C–H bond by other functional groups, and the development of new catalysts. |
| Databáze: | OpenAIRE |
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