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題名: | Robust and Electron-Rich cis-Palladium(II) Complexes with Phosphine and Carbene Ligands as Catalytic Precursors in Suzuki Coupling Reactions |
作者: | Liao, Chuang-Yi;Chan, Kai-Ting;Tu, Cheng-Yi;Chang, Yu-Wei;Hu, Ching-Han;Lee, Hon-Man |
貢獻者: | 化學系 |
日期: | 2009
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上傳時間: | 2012-05-03T06:18:07Z
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出版者: | John Wiley & Sons, Inc. |
摘要: | A new imidazolinium ligand precursor L(2)HCl (2) was prepared in 86 % yield. Compared with its imidazolium counterpart, L(1)HCl (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. |
關聯: | Chemistry - A European Journal, 15(2): 405-417 |
顯示於類別: | [化學系] 期刊論文
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