Addition reactions on coordinated olefinic ligands. II. Reaction between amines and monoolefins coordinated in cis-dichloro(olefin) (tert-phosphine)platinum(II) complexes

Enhancing Electrophilic Alkene Activation by Increasing the Positive Net Charge in Transition‐Metal Complexes and Application in Homogeneous Catalysis

“…Alkene complexes of palladium(ii) [23] and platinum(ii) [24] are known to be very susceptible for addition of amines and other nucleophiles; this has been widely investigated by several research groups, [25,26,27] see Equations (3) and (4).…”

Platinum‐Catalyzed Intermolecular Hydroamination of Alkenes: Halide‐Anion‐Promoted Catalysis

“…Since extensive information is available on the reactivity of Pt II -ethylene complexes with amines, [29][30][31][32][33][34] we were prompted to examine the possible catalytic hydroamination of ethylene with aniline in the presence of the newly developed [PtBr 2 ]/nBu 4 PBr system.…”

“…It should be noted that no zwitterionic complex has ever been evidenced from the reaction of aniline with any Pt II -ethylene complex. [29][30][31][32][33] This fact was explained by the insuf-ficient basicity of aniline (pK a = 4.63), relative to that of, for example, diethylamine (pK a Ͼ 10) for which the zwitterionic addition complex had been fully characterized.…”

“…In the case of Pt II alkene complexes, [29][30][31][32][33][34] attack by sufficiently basic amines (pK a of conjugated acid Ͼ 5) has been shown to afford zwitterionic complexes [Equation (4)], one of which could be characterized by X-ray dif-fraction study.…”

“…[30d] However, liberation of the alkylated amine by cleavage of the carbon-platinum bond needs a further step (reaction with HCl or NaBH 4 ) [Equation (5)], [30][31][32][33] so that the hydroamination reaction is only stoichiometric. [34] (4) (5) Soon after the publication of our paper on the Pt-catalyzed hydroamination of ethylene with aniline in ionic liquids (see below), [35] 4 ] has also been reported recently.…”