Synthesis, structures and catalytic activity of Pd(II) saccharinate complexes with monophosphines in direct arylation of five-membered heteroarenes with aryl bromides

YILMAZ V. T., Icsel C., Turgut O. R., AYGÜN M., Evren E., ÖZDEMİR İ.

INORGANICA CHIMICA ACTA, cilt.500, 2020 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 500
  • Basım Tarihi: 2020
  • Doi Numarası: 10.1016/j.ica.2019.119220
  • Dergi Adı: INORGANICA CHIMICA ACTA
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Chimica
  • Anahtar Kelimeler: Palladium(II), Saccharinate, Phosphine, Catalysis, Arylation, Heteroarenes, PD-IMIDATE COMPLEXES, PALLADIUM COMPLEXES, EFFICIENT CATALYSTS, COUPLING REACTIONS, LIGANDS, FUNCTIONALIZATION, NUCLEOSIDES, MECHANISM, CARBENE, HALIDES
  • Karadeniz Teknik Üniversitesi Adresli: Hayır

Özet

A number of new Pd(II) saccharinate (sac) complexes bearing a range of phenyl (Ph), cyclohexyl (Cy) and alkyl (Me and Et) substituted tertiary phosphine ligands with systematically changing electronic and steric properties, namely trans-[PdCl(sac)(L)(2)] (L = PPh3 (1); PPh2Cy (3)), trans-[Pd(sac)(2)(H2O)(L)] (L = PPh3 (2); PPh2Cy (5)), trans-[Pd(sac)(2)(L)(2)] (L = PPh2Cy (4); PPhCy2 (6); PCy3 (8)), [PdCl(sac)(PCy3)(DMSO)] (7), trans-[Pd (sac)(2)(PPh2Me)(DMSO)] (9) and cis-[M(sac)(2)(L)(2)] (L= PPhMe2 (10); PPh2Et (11); PPhEt2 (12)), were synthesized and structurally characterized. The Pd(II) complexes were applied for direct C2/C5 arylation of fivemembered heteroarenes such as furan, thiophene and thiazole derivatives with aryl bromides. Notably, arylation products up to 99% yields were obtained in the presence of the Pd(II) complexes. The catalytic mechanism of the direct arylation was proposed to proceed via a Pd(0)/Pd(II) pathway, due to elimination of the sac ligand in the Pd(II) complexes during catalysis.