Abstract
Reactions of [PdX2(dppm)] (X = Cl, Br) with a range of Grignard reagents have been investigated. Diorganopalladium complexes of the type [PdR2(dppm)] were obtained in good yield with the bulky mesityl or trimethylsilylmethyl groups, provided the reactions were performed using high Grignard:Pd ratios in ether solution. With the smaller R groups Me, Et, Bu, and CH2Ph, only the halide-bridged A-frame complexes [Pd2R2(μ-X)(μ-dppm)2]+ were formed, irrespective of the reaction conditions. Mixtures of chloride- and bromide-bridged complexes were produced when [PdCl2(dppm)] was treated with RMgBr, so [PdBr2(dppm)] was used as the starting material in certain cases. The mesityl derivative [Pd2(C6H2Me3)2(μ-Br)(μ-dppm)2]+ could be obtained from the reaction of [PdBr2(dppm)] with 4 mol equiv of C6H2Me3MgBr in CH2Cl2 solution, but with Me3SiCH2MgCl mixtures of monomeric and dimeric complexes were obtained under these conditions. The A-frame complex [Pd2(CH2SiMe3)2(μ-Cl)(μ-dppm)2]+ was generated, however, by reaction o...
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