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Mechanistic Studies of Pt(II)- and Au(I)-Catalyzed Hydrofunctionalization Reactions
- Abstract:
A thorough mechanistic understanding of transition metal catalyzed transformations advances development of improved synthetic methods for biologically active molecules. For the Pt(II) catalyzed hydroamination reaction, kinetic analysis of resting-state Pt heterobicyclic amine complex protonolysis was in accord with first order dependence of the rate on [Pt], zero order dependence on [R3N•HBF4], and 1/[Cl ] dependence. Comparison of these results to kinetic analysis of zwitterionic intermediate protonolysis suggested that the heterobicyclic amine complex must undergo rate limiting ligand dissociation followed by rapid intermolecular protonolysis in the catalytic hydroamination reaction.
In addition, novel cationic gold(I) -alkene complexes, which are proposed intermediates in a number of gold(I)-catalyzed hydrofunctionalization reactions, have been generated and characterized. Solution phase thermodynamic studies and X-ray crystallographic data revealed that the binding interaction is largely dominated by alkene to gold -donation. Kinetic analysis of degenerate alkene exchange is in accord with an associative exchange mechanism.
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