Platinum complexes, hydroaminations

Racemic NHC platinum complex (146) has been developed as a precatalyst for the intramolecular hydroamination of olefins with pending secondary alkylamine groups... 

A different catalytic cycle for alkene hydroamination is initiated by the oxidative addition of the N-H bond to the metal, followed by insertion of the alkene into the metal-nitrogen bond and reductive elimination to form the amine. The oxidative addition of unactivated N-H bonds to platinum(O) complexes is thermodynamically unfavorable, so the catalytic cycle cannot be completed17, but the successful iridium(I)-catalyzed amination of norbornene with aniline has been reported18. 

Examples of the insertions of alkenes or alk5mes into metal-amido bonds are also rare. Examples of the insertions of alkenes into tihe M-N bonds of isolated amido complexes include the reaction of a rhodium anilide complex with alkenes to form imines witii kinetic behavior that is consistent with migratory insertion,and the formal insertion of the strongly electrophilic acrylonitrile into a platinum anilide. Additional examples include reactions of a lanthanide-amido complex generated in situ, a catalytic carboamination process in which the stereochemistry implies insertions of olefins into amides, and a catalytic hydroamination that appears to occur through an aminoalkyl complex generated by S3m addition of the iridium and amido groups across the C=C bond of norbomene. 

Krogstad DA, Owens SB, Halfen JA, Young VG Jr (2005) Intramolecular hydroamination of alkynylamines in aqueous media catalyzed by platinum(II) l,3,5-triaza-7-phosphaadamantane (PTA) complexes. Inorg Chem Commun 8 65-69... 

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