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| - Insertion of Isocyanides across the Pd−C Bond in Alkyl or ArylPalladium(II) Complexes Bearing Mixed Nitrogen−Sulfur andNitrogen−Phosphorus Ancillary Ligands. The Mechanism ofReaction
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| - An exhaustive study dealing with the kinetic and mechanistic behavior of alkyl- and arylpalladiumcomplexes bearing pyridyl−thioethers (NS−R) and quinoline−phosphines (NP) as ancillary ligands whenreacting with 2,6-dimethyl isocyanide (DIC) and tosylmethyl isocyanide (TosMIC) was undertaken. Inthese reactions some differently substituted isocyanides insert into the palladium−carbon bond of alkyland aryl complexes bearing mixed (NS or NP) ligands. The reactions were carried out under equimolecularconditions since such a restrictive approach allows the determination of the rate constants related to theisocyanide insertion attack. Reactions carried out under nonstoichiometric conditions were also takeninto account and the reaction products characterized. Usually the formation of an inserted bis-substitutedisocyanide halide derivative of palladium(II) was observed. In a particular case the formation of an imidoyldimer was detected. The structures of the monoinserted [Pd(NSt-Bu)(C(Tol)NR2)I] (NSt-Bu = 2-(tert-butylthiomethyl)pyridine) and of the dimer [Pd(CNR2)(C(NR2)Me)Cl]2 (R2 = 2,6-Me2C6H3) werereported.
- A study dealing with the kinetic and mechanistic behavior of alkyl- and arylpalladium complexes bearing pyridyl−thioethers (NS−R) and quinoline−phosphines (NP) as ancillary ligands when reacted with 2,6-dimethyl isocyanide (DIC) and tosylmethyl isocyanide (TosMIC) was undertaken with the aim of determining the reaction rates and elucidating the intimate mechanism involved when differently substituted isocyanides insert into the palladium−carbon bond of alkyl and aryl complexes bearing mixed (NS or NP) ligands.
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