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Journal ArticleDOI

Reversible oxidative addition of triphenylphosphine to zero-valent nickel and palladium complexes

01 Jul 1976-Journal of the American Chemical Society (American Chemical Society)-Vol. 98, Iss: 15, pp 4499-4503
About: This article is published in Journal of the American Chemical Society.The article was published on 1976-07-01. It has received 91 citations till now. The article focuses on the topics: Triphenylphosphine & Palladium.
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Journal ArticleDOI
TL;DR: Nickel-Catalyzed Cross-Couplings Involving Carbon-Oxygen Bonds Brad M. Rosen, Kyle W. Quasdorf, Daniella A. Wilson, Na Zhang, Ana-Maria Resmerita, Neil K. Garg, and Virgil Percec report on cross-coupling strategies for high-performance liquid chromatography of carbon dioxide and nitrogen.
Abstract: Nickel-Catalyzed Cross-Couplings Involving Carbon-Oxygen Bonds Brad M. Rosen, Kyle W. Quasdorf, Daniella A. Wilson, Na Zhang, Ana-Maria Resmerita, Neil K. Garg,* and Virgil Percec* Roy & Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States

1,100 citations

Journal ArticleDOI
TL;DR: In this article, the aryl−aryl interchange reaction of ArPdL2I complex 1m was found to follow pseudo-first-order kinetics, suggesting that a dissociative pathway was involved.
Abstract: The aryl−aryl interchange reaction of ArPdL2I complex 1m was found to follow pseudo-first-order kinetics. A marked inhibition in the presence of excess phosphine and/or excess iodide was observed, suggesting that a dissociative pathway was involved, contrary to the analogous alkyl−aryl interchange reaction studied previously. Phosphine flooding experiments could not be performed due to a competing phosphonium salt formation reaction that occurred in the presence of excess phosphine. A deuterium labeling experiment indicated that the interchange reaction proceeded via the reductive elimination to form the phosphonium salt, suggesting that excess phosphine was acting as a trap for intermediate palladium(0) species preventing the generation of the interchanged palladium(II) complex. Substituent effect studies of the interchange reaction indicated that it was inhibited by electron-withdrawing groups on both the phosphine and palladium-bound aryl groups and by increased steric bulk on both the phosphine and pa...

260 citations

Journal ArticleDOI
TL;DR: In this paper, the reaction of KOCH2CMe3 with [(R)-Tol-BINAP]Pd(p-C6H4CN)Br formed [(R]-Tol BINAP]-PdP-C 6H 4CN(OCH2cMe3) (5) in quantitative yield (1H NMR spectroscopy) Thermolysis of 5 in THF-d8 at 47 °C led to C−O
Abstract: Reaction of KOCH2CMe3 with [(R)-Tol-BINAP]Pd(p-C6H4CN)Br formed [(R)-Tol-BINAP]Pd(p-C6H4CN)(OCH2CMe3) (5) in quantitative yield (1H NMR spectroscopy) Thermolysis of 5 in THF-d8 at 47 °C led to C−O

146 citations

Journal ArticleDOI
TL;DR: Theoretical studies of F/Ph exchange with the [(PH(3))(2)(PH(2)Ph)RhF] model system pointed to two possible mechanisms: (i) Ph transfer to Rh followed by F transfer to P (formally oxidative addition followed by reductive elimination, pathway 1) and (ii) Ftransfer to produce a metallophosphorane with subsequent PhTransfer to Rh (pathway 2).
Abstract: The fluoride congener of Wilkinson's catalyst, [(Ph3P)3RhF] (1), has been synthesized and fully characterized. Unlike Wilkinson's catalyst, 1 easily activates the inert C−Cl bond of ArCl (Ar = Ph, p-tolyl) under mild conditions (3 h at 80 °C) to produce trans-[(Ph3P)2Rh(Ph2PF)(Cl)] (2) and ArPh as a result of C−Cl, Rh−F, and P−C bond cleavage and C−C, Rh−Cl, and P−F bond formation. In benzene (2−3 h at 80 °C), 1 decomposes to a 1:1 mixture of trans-[(Ph3P)2Rh(Ph2PF)(F)] (3) and the cyclometalated complex [(Ph3P)2Rh(Ph2PC6H4)] (4). Both the chloroarene activation and the thermal decomposition reactions have been shown to occur via the facile and reversible F/Ph rearrangement reaction of 1 to cis-[(Ph3P)2Rh(Ph)(Ph2PF)] (5), which has been isolated and fully characterized. Kinetic studies of the F/Ph rearrangement, an intramolecular process not influenced by extra phosphine, have led to the determination of Ea = 22.7 ± 1.2 kcal mol-1, ΔH ⧧ = 22.0 ± 1.2 kcal mol-1, and ΔS ⧧ = −10.0 ± 3.7 eu. Theoretical studi...

131 citations

Journal ArticleDOI
TL;DR: In this paper, it was shown that the complexes 1e and 1f, synthesized independently by halogen-exchange from the iodo derivatives, undergo a facile aryl-aryl exchange between the palladium center and the coordinated phosphine ligands, just in contrast to 1a-c.

80 citations