Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands.

Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands. Research Abstract Details 

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Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands. Abstract Text:

Fabiola Barrios-Landeros,John F Hartwig,

We report an example of a bisphosphine palladium(0) complex with hindered ligands that undergoes oxidative addition of chloro-, bromo-, and iodoarenes in high yield. Addition of PhX (X = I, Br, Cl) to [Pd(Q-phos-tol)2] produced [Pd(Q-phos-tol)(Ph)(I)], [Pd(Q-phos-tol)(Ph)(Br)], and [Pd(Q-phos-tol)(Ph)(Cl)]2. To study the mechanisms of the oxidative addition of the three haloarenes to [Pd(Q-phos-tol)2], we determined the order of the reaction on the concentration of ligand and haloarene. The different haloarenes reacted through different mechanistic pathways. Addition of iodobenzene occurred by irreversible associative displacement of a phosphine. Addition of bromobenzene occurred by rate-limiting dissociation of phosphine. Addition of chlorobenzene occurred by reversible dissociation of phosphine, followed by rate-limiting oxidative addition. The mechanism of exchange of ligands from the Pd(0)L2 was also studied. The rate constant value for dissociation of ligand calculated from ligand exchange experiments is in agreement with the value calculated through experiments on oxidative addition.

Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands. Publishing Authors By Initials

F Barrios-Landeros,JF Hartwig,

For similar inorganic chemicals: phosphorus compounds: phosphines research abstracts see: inorganic chemicals: phosphorus compounds: phosphines research

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Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Journal of the American Chemical Society

VOLUME: 127

Page Numbers: 6944-5

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 18

MONTH: May

YEAR: 2005

Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands. Information

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LANGUAGE: eng

NlmUniqueID: 7503056

Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands. Keywords Mesh Terms:

KEYWORDS: Phosphines

MESH TERMS: chemistry

Chemical & Substance for Abstract: Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands. Information

Substance Name: Palladium

Registry Number: 7440-05-3

Grant and Affiliation Information for Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands.

AFFILIATION: Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM 58108

ACRONYM: GM

MEDLINETA: J Am Chem Soc

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