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Robust and Electron‐Rich cis ‐Palladium(II) Complexes with Phosphine and Carbene Ligands as Catalytic Precursors in Suzuki Coupling Reactions
Author(s) -
Liao ChuangYi,
Chan KaiTing,
Tu ChengYi,
Chang YuWei,
Hu ChingHan,
Lee Hon Man
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200801296
Subject(s) - carbene , phosphine , chemistry , palladium , aryl , ligand (biochemistry) , catalysis , ring (chemistry) , medicinal chemistry , coupling reaction , suzuki reaction , polymer chemistry , photochemistry , organic chemistry , alkyl , biochemistry , receptor
Abstract A new imidazolinium ligand precursor [L 2 H]Cl ( 2 ) was prepared in 86 % yield. Compared with its imidazolium counterpart, [L 1 H]Cl ( 1 ), 2 is very sensitive to moisture and can undergo ring‐opening reactions very readily. Palladium complexes with the ring‐opened products from imidazolinium salts were isolated and characterized by X‐ray crystallography. Theoretical studies confirmed that the imidazolinium salt has a higher propensity for the ring‐opening reaction than the imidazolium counterpart. New mixed phosphine/carbene palladium complexes, cis ‐[PdCl 2 (L)(PR 3 )] (L=L 1 and L 2 ; R=Ph, Cy), were successfully prepared. These complexes are highly robust as revealed by variable‐temperature NMR spectroscopic studies and thermal gravimetric analysis. The structural and electronic properties of the new complexes on varying the carbene group (imidazol‐2‐ylidene group (unsaturated carbene) vs. imidazolin‐2‐ylidene (saturated carbene)) and the phosphine group (PPh 3 vs. PCy 3 ) were studied in detail by X‐ray crystallography, X‐ray photoelectron spectroscopy, and theoretical calculations. The catalytic study reveals that cis ‐[PdCl 2 (L 2 )(PCy 3 )] is a competent Pd II precatalyst for Suzuki coupling reactions, in which unreactive aryl chlorides can be applied as substrates.