Linear Oligomerization of olefins via nickel chelate complexes and mechanistic considerations based on semi-empirical calculations

Keim, Wilhelm; Hoffmann, Bernd; Lodewick, R.; Peuckert, M.; Schmitt, Günter; Fleischhauer, Jörg; Meier, Ursula

doi:10.1016/0304-5102(79)80016-4

Cited by 107 publications

(43 citation statements)

References 27 publications

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“…[3] by analogy with the commonly accepted (4, 5 ) intramolecular addition of the Ni-H bond across a coordinated olefinic bond and hydrogenolysis to regenerate Ni-H complex 10. Elimination of a Ni-H moiety in Ni-alkyl complexes, such as 11, is apparently facile at ambient temperature or even lower (10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20): such processes are the source of Ni-H catalysed isomerization of olefins (9)(10)(11)(12). The hydrogenolysis of 11 requires a vacant coordination site to accommodate oxidative addition of hvdrogen followed by reductive elimination to give products and the regeneration of 10.…”

Section: Discussionmentioning

confidence: 99%

“…The observed clean chemoselectivitv in the present photohydrogenation is the consequence of a complex overall effect consisting of various factors, such as the ability of olefins to coordinate, the facility of nickel complex 11 to undergo hydrogenolysis, and other steric and excitation factors. Furthermore, the addition of a Ni-H bond to an unsymmetrical olefinic bond should be regioselective by analogy with catalysed oligomerization of terminal olefins (14)(15)(16)(17). This question will not be considered as it does not show in the products.…”

Section: Discussionmentioning

confidence: 99%

“…We wish to report that the photoreduction conditions under slow purging of Hz also serves as catalytic hydrogenation of simple olefins. Among metal catalysed olefin reactions (4-8), Ni-H complexes are good homogeneous catalysts for skeletal rearrangements (9, lo), isomerization (1 1-13), oligomerization (14)(15)(16)(17)(18), and hydrogenation (19,20) of olefins under moderate pressure and temperature. Examples of light-promoted catalysis with other metal complexes in hydrogenation of olefins are also known and nicely summarized in recent reviews (7,8).…”

Section: Introductionmentioning

confidence: 99%

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Light-promoted catalytic hydrogenation of olefins with nickel complexes: the formation of nickel hydrides from the reaction of Ni(I) complexes with hydrogen

Chow¹,

Li²,

Yang³

1988

Can. J. Chem.

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The conditions pertaining to triplet excited state ketone-sensitized photoreduction of Ni(acac)., under hydrogen were shown to serve as a method for light-promoted hydrogenation of olefins with clean chemospecificity. For example, the double bond in the bicyclic system was preferentially hydrogenated over the other double bond in dicyclopentadiene and in 5-methylenebicyclo-[2.2. llheptene. This photohydrogenation could be run under a wide range of conditions and was apparently a homogeneous catalytic process; in a late stage of photohydrogenation, concurrence of heterogeneous catalytic processes was not ruled out. The Ni(1) complexes of tetrahydrofuran and olefins generated from the photoreduction of N i ( a~a c )~ were shown to react with hydrogen to give nickel hydride complexes. By analogy with the generally accepted reaction pattern, coordinated olefins in these nickel hydride complexes probably spontaneously undergo intramolecular addition to give Ni-alkyl complexes. It is suggested that these Ni-alkyl complexes are photoexcited to generate a vacant coordination site so that the reaction with hydrogen can proceed to give products and regenerate a nickel hydride catalyst.CHOW, Y. L., LI, H., et YANG, M-S. Can. J. Chem. 66,2920Chem. 66, (1988.On a dkmontrt que les conditions permettant d'effectuer la photorkduction du Ni(acac).,, sensibiliske par I'ktat excitt triplet de la cktone et effectuke sous I'influence de l'hydrogtne, peuvent servir de mkthode pour effectuer des hydrogknations d'olkfines amorckes par la lumitre et prtsentant une grande chtmospkcificitk. Par exemple, on a pu effectuer l'hydrogtnation prkfkrentielle de la double liaison du systtme bicyclique par rapport a I'autre double liaison du dicyclopentadikne et du mkthyltne-5 bicyclo[2,2,l]hepttne. Cette photohydrogtnation, qui est apparemment un processus catalytique homogtne, peut &tre rtaliske dans diverses conditions expkrimentales; dans la dernitre portion de la photohydroghation, il est possible que des processus catalytiques hktkrogtnes interviennent d'une faqon concurrente. On a dkmontrk que les complexes du Ni(1) avec le tktrahydrofuranne et les olkfines qui sont produits lors de la photorkduction du Ni(acac)., rkagissent avec I'hydrogtne pour donner des complexes d'hydrure de nickel. Par analogie avec le processus gknkralement accept6 pour cette reaction, on croit que les olkfines coordonnkes aux complexes d'hydrure de nickel subissent spontankment une addition intramolCculaire conduisant a des complexes de Ni-alkyle. On suggtre que ces complexes de Ni-alkyle sont photoexcitts pour gknkrer un site de coordination vacant qui permet a la rkaction avec I'hydrogtne de prockder pour donner les produits et pour rkgknkrer un catalyseur d'hydrure de nickel.[Traduit par la revue]

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Light-promoted catalytic hydrogenation of olefins with nickel complexes: the formation of nickel hydrides from the reaction of Ni(I) complexes with hydrogen

Chow¹,

Li²,

Yang³

1988

Can. J. Chem.

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“…S3). No coupling of carbon to fluorine in the 19 F{ 1 H} NMR spectra was observed; this is due to the low natural abundance of 13 C. However, the 13 C{ 1 H} NMR spectra of L5 and 5 showed coupling of the three fluorine atoms to the carbon atoms with the triflouromethyl substituents on the pyrazole resulting in quartets (Fig. S2).…”

Section: Synthesis Of Bismentioning

confidence: 96%

Symmetrically and unsymmetrically substituted bis(pyrazole)-palladium(II) and nickel(II) halides as Pre-catalysts for ethylene dimerization and Friedel-Crafts alkylation of toluene and benzene

Moeti¹,

Darkwa²

2016

S.Afr.j.chem.

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“…1) to give metal complexes catalytically active in the oligomerization of ␣-olefins such as ethylene, propylene, 1-butene, 1-hexene and 1-octene to predominantly linear products even in the absence of aluminum co-catalysts [1][2][3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Novel polymer-supported β-diketonate nickel catalysts for α-olefin activation

Benvenuti

Carlini

Galletti

et al. 1998

Polym. Adv. Technol.

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Styrene–divinylbenzene resins were used for the synthesis of different polymer‐bound β‐diketones, obtained by anchoring the chelating group through either the central or the lateral position. The heterogenized diketone ligand was subsequently reacted with Ni(COD)2 analogously to the corresponding homogeneous catalysts active in α‐olefin oligomerization. The heterogenized catalysts showed a good activity only when the central position of the chelate moiety was free. Heterogenization caused a significant change of selectivity: olefin oligomerization was accompanied by the formation of a large amount of polymeric products. This behavior is discussed in terms of steric effects caused by the bulky polymeric ligand. © 1998 John Wiley & Sons, Ltd.

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Linear Oligomerization of olefins via nickel chelate complexes and mechanistic considerations based on semi-empirical calculations

Cited by 107 publications

References 27 publications

Light-promoted catalytic hydrogenation of olefins with nickel complexes: the formation of nickel hydrides from the reaction of Ni(I) complexes with hydrogen

Light-promoted catalytic hydrogenation of olefins with nickel complexes: the formation of nickel hydrides from the reaction of Ni(I) complexes with hydrogen

Symmetrically and unsymmetrically substituted bis(pyrazole)-palladium(II) and nickel(II) halides as Pre-catalysts for ethylene dimerization and Friedel-Crafts alkylation of toluene and benzene

Novel polymer-supported β-diketonate nickel catalysts for α-olefin activation

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