Priprava in reaktivnost paladijevih kompleksov z nukleofilnimi ligandi

Ževart, Tisa (author), Gazvoda, Martin (mentor)

V sklopu magistrskega dela smo se ukvarjali s sintezo paladijevih kompleksov z nukleofilnimi ligandi. Sintetizirali smo štiri paladijeve komplekse z nukleofilnimi karboksilatnimi ligandi s splošno formulo Pd(PPh3)2(OCOR)2. Izhajali smo iz tetrakis(trifenilfosfin)paladija(0) in karboksilnih kislin. Pokazali smo, da enak kompleks nastane tudi s 4-nitrofenolom. Preučevali smo reaktivnost sintetiziranih kompleksov pri reakcijah transmetalacije s paladijevimi oksidativnimi adukti. Pri teh eksperimentih smo uporabili paladijev kompleks z aril halogenidom Pd(PPh3)2(4-C6H4CHO)Br. Pripravili smo tudi oksidativni adukt Pd(PPh3)2(CH2SCH3)Cl in preizkusili njegovo reaktivnost pri reakcijah transmetalacije. Pokazali smo, da transmetalacija, zamenjava ligandov, med kompleksom Pd(PPh3)2(OCOCH2Cl)2 in obema zgoraj opisanima oksidativnima aduktoma poteče in da pri tem nastaneta dva nova paladijeva kompleksa. Produkta transmetalacije Pd(PPh3)2(OCOCH2Cl)X, X = Br, Cl smo izolirali in z rentgensko difrakcijsko analizo določili njuno strukturo.

• Language: Slovenian
• Keywords: organokovinska kemija, paladij, karboksilatni ligandi, transmetalacija
• Work type: Master's thesis/paper
• Typology: 2.09 - Master's Thesis
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Year: 2019
• PID: 20.500.12556/RUL-109535
• COBISS.SI-ID: 1538324931
• Publication date in RUL: 05.09.2019

Secondary language

• Language: English
• Title: Synthesis and reactivity of palladium complexes with nucleophilic ligands

Abstract

This master thesis focuses on the synthesis of palladium complexes with nucleophilic ligands. Four complexes bearing carboxylate ligands of the general formula Pd(PPh3)2(OCOR)2 were synthesised. Tetrakis(triphenyphosphine)palladium(0) and carboxylic acids were used as starting material. We showed that similar complex is formed with acidic 4-nitrophenol. We studied the reactivity of synthesised palladium complexes in transmetallation reactions with palladium oxidative adducts. For these experiments palladium complex with aryl halide Pd(PPh3)2(C6H4CHO)Br was used. Oxidative adduct Pd(PPh3)2(CH2SCH3)Cl was also synthesised and its reactivity in transmetallation reaction was tested. We showed that transmetallation – the transfer of ligands – between palladium complex Pd(PPh3)2(OCOCH2Cl)2 and oxidative adducts mentioned above takes place and that two new palladium complexes are formed. Transmetallation products of these reactions, namely Pd(PPh3)2(OCOCH2Cl)X, X = Br, Cl were isolated and their structures were determined by X-ray analysis.

• Keywords: organometallic chemistry, palladium, carboxylate ligands, transmetallation