Olefin oligomerization on nickel. A theoretical study of the barrier to olefin rotation and insertion

Trzcinska, Barbara M.; Fackler, John P.; Anderson, Alfred B.

doi:10.1021/om00080a027

Cited by 19 publications

(4 citation statements)

References 2 publications

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“…According to their calculations, insertion from a four-coordinate intermediate is preferred. More recent calculations support these results. , In accord with this finding, intramolecular alkene insertions into carbalkoxy−palladium bonds have been shown to proceed from four-coordinate intermediates . Very recently, Brookhart et al reported the formation of [Pd(C 2 H 4 C(O)Me)(phen)]BAr 4 (Ar = 3,5-(CF 3 ) 2 C 6 H 3 ) upon warming a solution of [Pd(C(O)Me)(η 2 -C 2 H 4 )(phen)]BAr 4 from −78 to −46 °C, which also shows that insertion occurs from a four-coordinate species …”

Section: Introductionmentioning

confidence: 71%

Kinetic Study of the Insertion of Norbornadiene into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(arylimino)acenaphthene

et al. 1997

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Kinetic study of the insertion of norbornadiene into palladium-carbon bonds of complexes containing the rigid bidentate nitrogen ligand Bis(arylimino)acenaphtene Groen, J.H.; Delis, J.G.P.; van Leeuwen, P.W.N.M.; Vrieze, K. Published in: Organometallics DOI:10.1021/om960789fLink to publication Citation for published version (APA):Groen, J. H., Delis, J. G. P., van Leeuwen, P. W. N. M., & Vrieze, K. (1997). Kinetic study of the insertion of norbornadiene into palladium-carbon bonds of complexes containing the rigid bidentate nitrogen ligand Bis(arylimino)acenaphtene. Organometallics, 16, 68-77. DOI: 10.1021/om960789f General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. complexes (1b-12b), bearing the bidentate nitrogen ligand bis(arylimino)acenaphthene (Ar-BIAN), have been synthesized via reaction of the corresponding neutral acylpalladium complexes Pd(C(O)R)X(Ar-BIAN) (1a-12a) with norbornadiene (nbd). For the first time, an extensive kinetic study of this migratory alkene insertion into acyl-palladium bonds of neutral complexes containing R-diimine ligands has been carried out. It has been found that under pseudo-first-order circumstances these reactions follow the rate law k obsd ) k 1 + k 2 [nbd], which shows that these reactions proceed via a pathway independent of alkene concentration (k 1 pathway) and a pathway dependent on alkene concentration (k 2 pathway). The dramatic decrease of the rate constants k 1 and k 2 upon increasing the steric bulk of the BIAN ligand and the large negative entropy of activation and low enthalpy of activation for both pathways indicate that the k 1 and k 2 pathways are closely related and involve associative processes. From the influence of solvent, X and C(O)R ligand, steric and electronic properties of the BIAN ligand, the presence of free halide and free BIAN, and the parameters of activation, mechanisms have been proposed for both pathways. The k 1 pathway may proceed via a rate-determining solvent-assisted halide or nitrogen dissociation, followed by alkene association and migratory insertion, while the k 2 pathway may occur via a rate-determining migratory alkene insertion in a contact ion pair intermediate. This species may be formed via alkene association followed by either halide or nitrogen dissociation.

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Section: Introductionmentioning

confidence: 71%

Kinetic Study of the Insertion of Norbornadiene into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(arylimino)acenaphthene

et al. 1997

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“…As alkenes are known to be good ligands for nickel, their effect on the above-mentioned reaction mechanism was also investigated in detail. In fact, while olefin coordination helps to stabilize Ni(0) species (Δ G = −46.3 kcal/mol for Ni(0)–olefin complex A′ , see SI), a mechanism involving the addition of alkyl radicals onto the Ni(II)–olefin complex B′ (Δ G = 21.8 kcal/mol) via TS D‑F (Δ G ⧧ = 15.4 kcal/mol, Scheme d, path b) is substantially disfavored compared to the direct addition onto the free olefin (Δ G = −1.3 kcal/mol via TS D‑E Δ G ⧧ = 19.5 kcal/mol) followed by recombination with the PhNi II species B to give alkyl Ni(III) complex F (Scheme d, path a).…”

Section: Results and Discussionmentioning

confidence: 99%

Ni-Catalyzed Reductive Dicarbofunctionalization of Nonactivated Alkenes: Scope and Mechanistic Insights

et al. 2019

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Olefins devoid of directing or activating groups have been dicarbofunctionalized here with two electrophilic carbon sources under reductive conditions. Simultaneous formation of one C(sp 3 )−C(sp 3 ) and one C(sp 3 )−C(sp 2 ) bond across a variety of unbiased π-systems proceeds with exquisite selectivity by the combination of a Ni catalyst with TDAE as sacrificial reductant. Control experiments and computational studies revealed the feasibility of a radical-based mechanism involving, formally, two interconnected Ni(I)/Ni(III) processes and demonstrated the different ability of Ni(I) species (Ni(I)I vs PhNi(I)) to reduce the C(sp 3 )−I bond. The role of the reductant was also investigated in depth, suggesting that a oneelectron reduction of Ni(II) species to Ni(I) is thermodynamically favored. Further, the preferential activation of alkyl vs aryl halides by ArNi(I) complexes as well as the high affinity of ArNi(II) for secondary over tertiary C-centered radicals explains the lack of undesired homo-and direct coupling products (Ar−Ar, Ar−Alk) in these transformations.

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“…Ni(SacSac)ClPR 3 and its chemistry 30 got me interested in Zeigler-Natta catalysts. As a result I consulted with BFGoodrich and Firestone (now Bridgestone) for many years on Zeigler elastomer polymerization catalysis, 31 and on metal-sulfur chemistry related to vulcanization 32 and the adhesion of rubber to steel belts. This is copper-sulfur chemistry since the steel cord in tires is coated with copper which bonds to the sulfur linkages in the vulcanized rubber.…”

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confidence: 99%

“…A large single crystal showed no significant conductivity, however. Very recently, we have determined by 31 P HOESY and PGSE NMR that aggregation of these TR(carb) and TR(bzim) species with [Hg(C 6 F 4 )] 3 occurs in solution. 100 Much remains to be understood regarding the luminescence of Au(I) complexes, but it is clear that aurophilic interactions influence strongly emission behavior.…”

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confidence: 99%

Forty-Five Years of Chemical Discovery Including a Golden Quarter-Century

2002

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Inorganic chemistry became a passion for me as a graduate student in the 1950s. It was exciting to be part of the renaissance of the discipline, and I am pleased to have contributed to its strength. Physical concepts applied to the understanding of the properties of transition metal compounds guided our work initially. In the 1970s, probably as a direct result of the world abandoning the gold standard, the chemistry of gold was awakened after a long sleep. Much of the chemistry covered in this review of our work relates to novel compounds of gold and the properties they display which have been uncovered during the last 25 years of the 20th century. Stable metal-metal bonded Au(II) and organometallic Au(III) compounds, bi- and trimetallic oxidative addition, phosphorescent species with microsecond lifetimes, gold chains resulting from aurophilic bonding stronger than H-bonding, and recently, gold binding to organic pi acids have intrigued my group and other gold chemists during this period.

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Olefin oligomerization on nickel. A theoretical study of the barrier to olefin rotation and insertion

Cited by 19 publications

References 2 publications

Kinetic Study of the Insertion of Norbornadiene into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(arylimino)acenaphthene

Kinetic Study of the Insertion of Norbornadiene into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(arylimino)acenaphthene

Ni-Catalyzed Reductive Dicarbofunctionalization of Nonactivated Alkenes: Scope and Mechanistic Insights

Forty-Five Years of Chemical Discovery Including a Golden Quarter-Century

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