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• W2017422969 abstract "Reactions of [Pd2Cl2(μ-dppm)2] with RMgX (R = Me, Et, Bu, Ph, C6H4Me-4) at low temperature, followed by addition of CBr4 and excess NH4PF6 or 1 equiv of TlPF6, provided halide-bridged organopalladium A-frame complexes of the form [Pd2R2(μ-X)(μ-dppm)2]PF6. Mixed metal complexes were obtained similarly starting from [PdPtCl2(μ-dppm)2]. Unsymmetrical A-frames of the type [Pd2(C6H2Me3-2,4,6)R(μ-Cl)(μ-dppm)2]+ were generated by reaction of [Pd(C6H2Me3-2,4,6)(dppm)2]+ (obtained by treatment of [PdCl2(cod)] with mesitylmagnesium bromide at low temperature, followed by 2 equiv of dppm) with [Pd2R2(μ-Cl)2(AsPh3)2]. The organopalladium A-frames did not react readily with CO, but the corresponding acyl derivatives [Pd2(COR)2(μ-Cl)(μ-dppm)2]PF6 were produced by carbonylation of [Pd2R2(μ-Cl)2(AsPh3)2] followed by addition of dppm (R = Me, Et, Bn). Thermal decomposition of [Pd2(CH2Ph)2(μ-Cl)(μ-dppm)2]Cl was found to be first order in A-frame and resulted in quantitative formation of [Pd2Cl2(μ-dppm)2] and 1,2-diphenylethane. The methyl and aryl complexes underwent both reductive elimination and hydrogen abstraction reactions. [Pd2Et2(μ-Br)(μ-dppm)2]PF6 decomposed by β-hydride elimination and subsequent reductive elimination to yield ethene and ethane, whereas the butyl derivative gave both 1- and 2-butene. Acetic acid was formed when [Pd2(COMe)2(μ-Cl)(μ-dppm)2]PF6 was heated in dmso-d6 solution, but decarbonylation was the predominant process in dioxane. The molecular structures of [Pd2(CH2Ph)2(μ-Br)(μ-dppm)2]PF6·H2O,2C6H6 and [Pd2Cl2(μ-Cl)(μ-dppm)2]OH·0.5(CH3)2CO are also described." @default.
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• W2017422969 date "2001-11-01" @default.
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• W2017422969 title "General Route to Halide-Bridged Organopalladium A-Frame Complexes and Studies of Reductive Elimination from These Bimetallic Systems" @default.
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• W2017422969 doi "https://doi.org/10.1021/om010626d" @default.
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