Synthesis, structures and catalytic activity of Pd(II) saccharinate complexes with monophosphines in direct arylation of five-membered heteroarenes with aryl bromides
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Date
2020-01-24
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Elsevier Science
Abstract
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.
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Keywords
Chemistry, Palladium(II), Saccharinate, Phosphine, Catalysis, Arylation, Heteroarenes, PD-imidate complexes, Palladium complexes, Efficient catalysts, Coupling reactions, Ligands, Functionalization, Nucleosides, Mechanism, Carbene, Halides, Aromatic compounds, Catalysis, Catalyst activity, Chlorine compounds, Ligands, Metal halides, Phosphorus compounds, Quantum chemistry, Synthesis (chemical), Arylations, Thiazole derivatives, Catalytic mechanisms, Heteroarenes, Phosphine, Saccharinate, Steric properties, Tertiary phosphines, Palladium compounds
Citation
Yılmaz, V. T. vd. (2020). "Synthesis, structures and catalytic activity of Pd(II) saccharinate complexes with monophosphines in direct arylation of five-membered heteroarenes with aryl bromides". Inorganica Chimica Acta, 500.