Dialkylpalladium complexes

The reductive elimination and the /S-H elimination are competitive. The /S-H elimination takes place with trans dialkylpalladium complexes such as 36. The reductive elimination is favored by coordination of bidentate phosphine ligands which have larger bite angles (for the effect of bite angles, see van Leeuwen et al. [24]) to force other mutually cis ligands closer. Thus bidentate ligands of... 

In the thermal decomposition of dimethylpalladium complex under CO, dimethyl diketone is produced together with acetonc. P The process of alkyl migration to coordinated CO in the reactions of cis- and trani-dialkylpalladium complexes has been established on the basis of the observation of the distribution of the products.P P P P ... 

Plate 1 A possible sequence of intermediates involved in asymmetric cross-coupling of a-methylbenzylmagnesium chloride with p-methoxy-p-bromostyrene, showing first the oxidative addition of the halide, and then the formation of a dialkylpalladium complex with reductive elimination in the final step. The molecular models were produced in Chem3D Plus, using literature crystallographic coordinates to generate the initial complex. 

The regioselective amination of 2,3-dihydrofuran with morpholine catalyzed by palladium thiocyanate diphosphine complexes (45 turnovers)102, and the regioselective addition of aniline to acrylonitrile and analogous electron-poor alkenes catalyzed by dialkylpalladium(dmpe) complexes (hundreds of turnovers)103 have recently been reported, but the scope of the reactions is limited to the specific type of alkene. 

The behavior of the trans- and c/.v-dialkylpalladium(II) complexes having p-hydrogens on thermolysis offer a striking contrast [76b]. Thus the trans isomers... 

The preparation of a number of dialkylpalladium(II) complexes of the type cis - or trans-[PdR2(PMe )oJ nd cis-[PdR2(dmpe)]... 

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