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Equilibrium Study of Pd(dba)2 and P(OPh)3 in the Pd-Catalyzed Allylation of Aniline by Allyl Alcohol.

ABSTRACT: Reaction of Pd(dba)2 and P(OPh)3 shows a unique equilibrium where the Pd[P(OPh)3]3 complex is favored over both Pd(dba)[P(OPh)3]2 and Pd[P(OPh)3]4 complexes at room temperature. At a lower temperature, Pd[P(OPh)3]4 becomes the most abundant complex in solution. X-ray studies of Pd[P(OPh)3]3 and Pd(dba)[P(OPh)3]2 complexes show that both complexes have a trigonal geometry with a Pd-P distance of 2.25 Å due to the π-acidity of the phosphite ligand. In solution, pure Pd(dba)[P(OPh)3]2 complex equilibrates to the favored Pd[P(OPh)3]3 complex, which is the most stable complex of those studied, and also forms the most active catalytic species. This catalyst precursor dissociates one ligand to give the reactive Pd[P(OPh)3]2, which performs an oxidative addition of nonmanipulated allyl alcohol to generate the π-allyl-Pd[P(OPh)3]2 intermediate according to ESI-MS studies.

SUBMITTER: Sawadjoon S 

PROVIDER: S-EPMC3893935 | biostudies-literature | 2014 Jan

REPOSITORIES: biostudies-literature

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Equilibrium Study of Pd(dba)<sub>2</sub> and P(OPh)<sub>3</sub> in the Pd-Catalyzed Allylation of Aniline by Allyl Alcohol.

Sawadjoon Supaporn S   Orthaber Andreas A   Sjöberg Per J R PJ   Eriksson Lars L   Samec Joseph S M JS  

Organometallics 20131231 1

Reaction of Pd(dba)<sub>2</sub> and P(OPh)<sub>3</sub> shows a unique equilibrium where the Pd[P(OPh)<sub>3</sub>]<sub>3</sub> complex is favored over both Pd(dba)[P(OPh)<sub>3</sub>]<sub>2</sub> and Pd[P(OPh)<sub>3</sub>]<sub>4</sub> complexes at room temperature. At a lower temperature, Pd[P(OPh)<sub>3</sub>]<sub>4</sub> becomes the most abundant complex in solution. X-ray studies of Pd[P(OPh)<sub>3</sub>]<sub>3</sub> and Pd(dba)[P(OPh)<sub>3</sub>]<sub>2</sub> complexes show that both complex  ...[more]

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