Palladium complexes with carbene and phosphine ligands: Synthesis, structural characterization, and direct arylation reactions between aryl halides and alkynes

Kai Ting Chan, Yi Hua Tsai, Wu Shien Lin, Jia Rong Wu, Shih Jung Chen, Fu Xing Liao, Ching-Han Hu, Hon Man Lee

Research output: Contribution to journalArticle

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Abstract

The new palladium complexes with NHC and phosphine ligands, cis-PdCl 2(L2)(PPh3) (2), cisPdBr2(L 2)(PPh3) (3), and cis-PdCl2(L 3)(PPh3) (4) were prepared following a general protocol of a one pot reaction between PdCl2(COD), PPh3, and the ligand precursors LH · Y (Y = Cl, Br, BF4) (L2 = l,3-dibenzylimidazolin-2-ylidene; L3 = l,3-dibenzylimidazol-2- ylidene). The cis-PdCl2(L3)(PCy3) complex (5) was prepared by the ligand substitution reaction between 4 and PCy3. The palladium complexes with NHC and pyridine complexes, trans-PdCl 2(L)(py) (6: L = L2; 7: L = L3) were obtained by heating a mixture Of PdCl2(COD) and LH · BF4 in pyridine. A similar reaction condition using CH3CN as solvent with KO'Bu as base afforded cis-PdCl2(L3)2 (8). Complexes 2-8 were successfully characterized by X-ray crystallographic studies, among which, intriguingly, two polymorphs of 8 were obtained. Thermogravimetric analysis showed that the Cis-PdX2(NHC)(PR3) complexes are more thermally stable than the trans-PdCl2(NHC)(py) complexes. Together with the known Cis-PdCl2(L1(PCy3) (1) (L1 = l-benzyl-3-(N-phenylacetamido)imidazol-2-ylidene), they were screened for the direct arylation reaction between aryl halides and alkynes. The result indicate that the carbene/phosphine complexes 1-5 are superior precatalysts than 6-8 with higher activities than the commonly-used system of Pd(OAc)2/2PPh3.

Original languageEnglish
Pages (from-to)463-472
Number of pages10
JournalOrganometallics
Volume29
Issue number2
DOIs
Publication statusPublished - 2010 Jan 25

Fingerprint

phosphine
Alkynes
Palladium
carbenes
alkynes
phosphines
halides
palladium
Ligands
ligands
crack opening displacement
synthesis
pyridines
imidazoles
substitutes
heating
carbene
palladium chloride
Polymorphism
Thermogravimetric analysis

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Chan, Kai Ting ; Tsai, Yi Hua ; Lin, Wu Shien ; Wu, Jia Rong ; Chen, Shih Jung ; Liao, Fu Xing ; Hu, Ching-Han ; Lee, Hon Man. / Palladium complexes with carbene and phosphine ligands : Synthesis, structural characterization, and direct arylation reactions between aryl halides and alkynes. In: Organometallics. 2010 ; Vol. 29, No. 2. pp. 463-472.
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abstract = "The new palladium complexes with NHC and phosphine ligands, cis-PdCl 2(L2)(PPh3) (2), cisPdBr2(L 2)(PPh3) (3), and cis-PdCl2(L 3)(PPh3) (4) were prepared following a general protocol of a one pot reaction between PdCl2(COD), PPh3, and the ligand precursors LH · Y (Y = Cl, Br, BF4) (L2 = l,3-dibenzylimidazolin-2-ylidene; L3 = l,3-dibenzylimidazol-2- ylidene). The cis-PdCl2(L3)(PCy3) complex (5) was prepared by the ligand substitution reaction between 4 and PCy3. The palladium complexes with NHC and pyridine complexes, trans-PdCl 2(L)(py) (6: L = L2; 7: L = L3) were obtained by heating a mixture Of PdCl2(COD) and LH · BF4 in pyridine. A similar reaction condition using CH3CN as solvent with KO'Bu as base afforded cis-PdCl2(L3)2 (8). Complexes 2-8 were successfully characterized by X-ray crystallographic studies, among which, intriguingly, two polymorphs of 8 were obtained. Thermogravimetric analysis showed that the Cis-PdX2(NHC)(PR3) complexes are more thermally stable than the trans-PdCl2(NHC)(py) complexes. Together with the known Cis-PdCl2(L1(PCy3) (1) (L1 = l-benzyl-3-(N-phenylacetamido)imidazol-2-ylidene), they were screened for the direct arylation reaction between aryl halides and alkynes. The result indicate that the carbene/phosphine complexes 1-5 are superior precatalysts than 6-8 with higher activities than the commonly-used system of Pd(OAc)2/2PPh3.",
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Palladium complexes with carbene and phosphine ligands : Synthesis, structural characterization, and direct arylation reactions between aryl halides and alkynes. / Chan, Kai Ting; Tsai, Yi Hua; Lin, Wu Shien; Wu, Jia Rong; Chen, Shih Jung; Liao, Fu Xing; Hu, Ching-Han; Lee, Hon Man.

In: Organometallics, Vol. 29, No. 2, 25.01.2010, p. 463-472.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Palladium complexes with carbene and phosphine ligands

T2 - Synthesis, structural characterization, and direct arylation reactions between aryl halides and alkynes

AU - Chan, Kai Ting

AU - Tsai, Yi Hua

AU - Lin, Wu Shien

AU - Wu, Jia Rong

AU - Chen, Shih Jung

AU - Liao, Fu Xing

AU - Hu, Ching-Han

AU - Lee, Hon Man

PY - 2010/1/25

Y1 - 2010/1/25

N2 - The new palladium complexes with NHC and phosphine ligands, cis-PdCl 2(L2)(PPh3) (2), cisPdBr2(L 2)(PPh3) (3), and cis-PdCl2(L 3)(PPh3) (4) were prepared following a general protocol of a one pot reaction between PdCl2(COD), PPh3, and the ligand precursors LH · Y (Y = Cl, Br, BF4) (L2 = l,3-dibenzylimidazolin-2-ylidene; L3 = l,3-dibenzylimidazol-2- ylidene). The cis-PdCl2(L3)(PCy3) complex (5) was prepared by the ligand substitution reaction between 4 and PCy3. The palladium complexes with NHC and pyridine complexes, trans-PdCl 2(L)(py) (6: L = L2; 7: L = L3) were obtained by heating a mixture Of PdCl2(COD) and LH · BF4 in pyridine. A similar reaction condition using CH3CN as solvent with KO'Bu as base afforded cis-PdCl2(L3)2 (8). Complexes 2-8 were successfully characterized by X-ray crystallographic studies, among which, intriguingly, two polymorphs of 8 were obtained. Thermogravimetric analysis showed that the Cis-PdX2(NHC)(PR3) complexes are more thermally stable than the trans-PdCl2(NHC)(py) complexes. Together with the known Cis-PdCl2(L1(PCy3) (1) (L1 = l-benzyl-3-(N-phenylacetamido)imidazol-2-ylidene), they were screened for the direct arylation reaction between aryl halides and alkynes. The result indicate that the carbene/phosphine complexes 1-5 are superior precatalysts than 6-8 with higher activities than the commonly-used system of Pd(OAc)2/2PPh3.

AB - The new palladium complexes with NHC and phosphine ligands, cis-PdCl 2(L2)(PPh3) (2), cisPdBr2(L 2)(PPh3) (3), and cis-PdCl2(L 3)(PPh3) (4) were prepared following a general protocol of a one pot reaction between PdCl2(COD), PPh3, and the ligand precursors LH · Y (Y = Cl, Br, BF4) (L2 = l,3-dibenzylimidazolin-2-ylidene; L3 = l,3-dibenzylimidazol-2- ylidene). The cis-PdCl2(L3)(PCy3) complex (5) was prepared by the ligand substitution reaction between 4 and PCy3. The palladium complexes with NHC and pyridine complexes, trans-PdCl 2(L)(py) (6: L = L2; 7: L = L3) were obtained by heating a mixture Of PdCl2(COD) and LH · BF4 in pyridine. A similar reaction condition using CH3CN as solvent with KO'Bu as base afforded cis-PdCl2(L3)2 (8). Complexes 2-8 were successfully characterized by X-ray crystallographic studies, among which, intriguingly, two polymorphs of 8 were obtained. Thermogravimetric analysis showed that the Cis-PdX2(NHC)(PR3) complexes are more thermally stable than the trans-PdCl2(NHC)(py) complexes. Together with the known Cis-PdCl2(L1(PCy3) (1) (L1 = l-benzyl-3-(N-phenylacetamido)imidazol-2-ylidene), they were screened for the direct arylation reaction between aryl halides and alkynes. The result indicate that the carbene/phosphine complexes 1-5 are superior precatalysts than 6-8 with higher activities than the commonly-used system of Pd(OAc)2/2PPh3.

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