Palladium Alkyl Complexes Containing β-Phosphonato−Phosphine P,O Ligands and Their Reactivity toward CO-Ethylene or -Acrylate Insertion
作者： Adel Hamada , Pierre Braunstein
DOI: 10.1021/OM801020E
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摘要: Neutral and cationic square-planar Pd(II) complexes containing the β-phosphonato-phosphine ligand rac-Ph2PCH(Ph)P(O)(OEt)2 (1) or new α-silyl-phosphonato-phosphine Ph2PCH(SiMe3)P(O)(OMe)2 (4) have been prepared. Reaction of 4 with [Pd(μ-Cl)(dmba)]2 (dmba = o-C6H4CH2NMe2) afforded an equilibrium mixture [Pd(dmba){Ph2PCH(SiMe3)P(O)(OMe)2}]Cl (5) [PdCl(dmba){Ph2PCH(SiMe3)P(O)(OMe)2}] (5′), which illustrates hemilabile behavior in this system. From stepwise insertion reaction CO ethylene into Pd−C bond [PdCl(Me){Ph2PCH(Ph)P(O)(OEt)2}] (2a), metallacyclic complex [Pd{CH2CH2C(O)Me{Ph2PCH(Ph)P(O)(OEt)2][BF4] (10) was obtained features first acetyl−ethylene coupling product a phosphine−phosphonate ligand. Chloride abstraction from 2a led to [PdMe(NCMe){Ph2PCH(Ph)P(O)(OEt)2}][BF4] (8), reacted sequentially methyl acrylate afford [Pd{CH[C(O)OMe][CH2C(O)Me]}{Ph2PCH(Ph)P(O)(OEt)2}][BF4] (11). The r...
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