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|標題:||Application of Tautomerism of Ferrocenyl Secondary Phosphine Oxides in Suzuki-Miyaura Cross-Coupling Reactions||作者:||Jung, L.Y.
|關鍵字:||phosphorus bonded hydrogen;catalyzed c-c;aryl chlorides;dialkyl;phosphonates;palladium catalysts;vinyl chlorides;boronic acids;complexes;ligands;diethylphosphonate||Project:||Organometallics||期刊/報告no：:||Organometallics, Volume 28, Issue 20, Page(s) 6044-6053.||摘要:||
Several new ferrocenyl secondary phosphine oxides, (eta(5)-C(5)H(4)-P(=O)(Ph)(H))(2)Fe (7aB) and (eta(5)-C(5)H(4)-P(=O)(R)(H))(eta(5)-C(5)H(5))Fe (7M, a: R = Ph; c: R = Cy), were prepared and characterized by spectroscopic means. Further reaction of Pd(COD)Cl(2) with 2 molar equiv of (eta(5)-C(5)H(4)-P(=O)-(R)(H)(2)Fe (7bM, b: R = (t)Bu) led to the formation of the palladium dimer [(7b'M)(7b'M-H(+))Pd(mu-Cl)](2), 8. In addition, the reaction of Pd(OAc)(2) With 1 molar equiv of 7bM yielded a bis-7bM-coordinated palladium acetate, [(7b'M)(7b'M-H(+))Pd(OAc)], 9. The molecular structures of 7aB, 7aM, 7bM, 8, and 9 were determined by single-crystal X-ray diffraction methods. A tautomeric equilibrium between 7aB and its isomeric form (eta(5)-C(5)H(4)-P(OH)(Ph))(2)Fe (7a'B) indeed took place. This was also true for the case of 7aM and its isomeric form (eta(5)-C(5)H(4)-P(OH)(Ph))(eta(5)-C(5)H(5))Fe (7a'M). Palladium-catalyzed Suzuki-Miyaura reactions employing 7aB and 7bM as ligands gave satisfactory results.
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