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The reaction in acetonitrile between PdCl2 and the carbonyl-stablized ylide Ph3PCHCO2Me. Synthesis of [P6H4)Ph2}(CO2Me)}(μ-Cl)]2 and some of its derivatives and of [PdCl2{CH(PPh3)CO2Me}2]

1989; Elsevier BV; Volume: 364; Issue: 3 Linguagem: Inglês

10.1016/0022-328x(89)87150-5

1872-8561

José Vicente, M.T. Chicote, Juan Fernández‐Baeza,

Synthetic Organic Chemistry Methods

Upon reaction of PdCl2 with the ylide Ph3PCHCO2Me in acetonitrile (12) at room temperature the complex [PdCl2{CH(PPh3)CO2Me}2] (1) separates. The same reaction at the reflux temperature gives the dinuclear complex [Pd{CH{P(2-C6H4)Ph2}(CO2Me)}(μ-Cl)]2 (2) along with the phosphonium salt [Ph3PCH2CO2-Me]Cl. Complex 1 is better obtained by reaction (12) of [PdCl2(NCC6H5)2] with the ylide at room temperature. Complex 2 reacts with PPh3 (12) or pyridine (py) (excess to give the products of bridge-splitting [Pd{CH{P(2-C6H4)Ph2}-(CO2Me)}Cl(L)] (L = PPh3 (3), L = py (4)). Complex 3 is also obtained when a 14 molar ratio of the reactants is used but, in the presence of NaClO4 the complex [Pd{CH{P(2-C6H4)Ph2}(CO2Me)}(PPh3)2]ClO4 (5) is obtained; complex 2 reacts with bidentate ligands LL in the presence of NaClO4 (1/2/3) to give [Pd{CH{P2-C6H4)Ph2}(CO2Me)}(LL)]ClO4 [LL = 2,2′-bipyridine (bipy) (6), 1,10-phenanthroline (phen) (7), and with Tlacac (12) (acacH = acetylacetone) to give [Pd{CH{P(2-C6H4)Ph2}(CO2Me)}(acac)] (8).