Nickel catalyzed dimerization reactions of vinylidene compounds: Head-to-head couplings and catalyst stabilization

Behr, Arno; Rentmeister, Nils; Seidensticker, Thomas; Faßbach, Thiemo A.; Peitz, Stephan; Maschmeyer, Dietrich

doi:10.1016/j.molcata.2014.08.043

Cited by 8 publications

(5 citation statements)

References 14 publications

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“…That is to say, the infrared spectrum of isobutene is more complex than that of isobutane. In addition, as the π-bonding orbital of the CC bond in the isobutene molecule is perpendicular to the C plane, it is generally the adsorption site for isobutene adsorbed on a metal surface . As hydrogenolysis of isobutane is changed into dehydrogenation due to the introduction of Sn, the adsorption states of isobutene are probably different on 4Ni/SiO 2 and 4Ni-Sn/SiO 2 .…”

Section: Resultsmentioning

confidence: 99%

Effect of Sn on Isobutane Dehydrogenation Performance of Ni/SiO₂ Catalyst: Adsorption Modes and Adsorption Energies of Isobutane and Isobutene

Zhu

Wang

Liu

et al. 2017

ACS Appl. Mater. Interfaces

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The reaction of isobutane over Ni/SiO catalyst changes from hydrogenolysis to dehydrogenation when Sn is introduced. The adsorption modes and energies of isobutane and isobutene over the Ni/SiO catalyst with and without Sn addition were determined by in situ FTIR and a novel transient response adsorption approach. In the absence of Sn, isobutane is adsorbed in a double-site mode with H atoms in two methyl groups of isobutane, facilitating hydrogenolysis of isobutane. After the addition of Sn, a single-site adsorption mode with the H atom in the methylidyne group is speculated instead, which is beneficial to the rupture of the C-H bond rather than the C-C bond. Moreover, the double-site adsorption mode of isobutene with the C═C bond and the H atom in a methyl group is turned into single-site mode with the C═C bond after the introduction of Sn. As for the adsorption energy of isobutene, the introduction of Sn leads to an obvious decrease from 74 to 50 kJ mol and facilitates the prompt desorption of isobutene, resulting in a high selectivity of 81.9 wt %.

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Section: Resultsmentioning

confidence: 99%

Effect of Sn on Isobutane Dehydrogenation Performance of Ni/SiO₂ Catalyst: Adsorption Modes and Adsorption Energies of Isobutane and Isobutene

Zhu

Wang

Liu

et al. 2017

ACS Appl. Mater. Interfaces

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“…For organonickel compounds, one possible pathway is reductive elimination leading to black nickel(0), as shown by Behr et al with fluorinated acetyacetonate-based complexes (Scheme ). A second step as a direct consequence is metalation leading to the bis-ligated inactive species. These two successive deactivation pathways have been reviewed by Matt et al for anionic (P,O)-ligands …”

Section: Active Sites and Mechanism(s)mentioning

confidence: 99%

Nickel Catalyzed Olefin Oligomerization and Dimerization

et al. 2020

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Brought to life more than half a century ago and successfully applied for high-value petrochemical intermediates production, nickel-catalyzed olefin oligomerization is still a very dynamic topic, with many fundamental questions to address and industrial challenges to overcome. The unique and versatile reactivity of nickel enables the oligomerization of ethylene, propylene and butenes into a wide range of oligomers that are highly sought-after in numerous fields to be controlled. Interestingly, both homogeneous and heterogeneous nickel catalysts have been scrutinized and employed to do this. This rare specificity encouraged us to interlink them in this review so as to open up opportunities for further catalyst development and innovation. An in-depth understanding of the reaction mechanisms in play is essential to being able to fine-tune the selectivity and achieve efficiency in the rational design of novel catalytic systems. This review thus provides a complete overview of the subject, compiling the main fundamental/industrial milestones and remaining challenges facing homogeneous/heterogeneous approaches as well as emerging catalytic concepts, with a focus on the last 10 years.

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“…One notable class of nickel catalysts was reported independently by Keim and Behr, whereby hexafluoroacetylacetonate (acac CF3 ) nickel complexes Ni-1 and Ni-2 were competent for the dimerization of isobutene (Scheme B). , The dimerization products were exclusively the less branched C 8 olefin isomers arising from C–C bond formation between two primary carbons through an isobutyl-nickel intermediate and insertion of a second isobutene in a selective 2,1 fashion (Scheme B), as compared to the more branched mixture obtained with traditional acid catalysis. A nickel-hydride complex was proposed as the active catalyst, likely formed from β-hydride elimination of the cyclooctenyl ligand of Ni-1 to generate 1,5-cyclooctadiene, which was observed by gas chromatography (GC) or generated in situ by addition of alkyl aluminum activator to Ni-2 . By virtue of its high electrophilicity and open coordination environment, these nickel precatalysts seemed well suited for the oligomerization of trisubstituted olefins that are typically unreactive toward oligomerization with transition metal catalysts (Scheme C).…”

Section: Introductionmentioning

confidence: 99%

Nickel-Catalyzed Dimerization of Di- and Trisubstituted Olefins

Yruegas

Paccagnini

et al. 2022

Organometallics

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The dimerization of a series of di-and trisubstituted C 5 -olefins catalyzed by hexafluoroacetylacetonate (acac CF3 ) nickel complexes is described. The dimerization of the trisubstituted olefin 2-methyl-2-butene by both a single-component nickel precatalyst and in situ activation of a bis(acac CF3 ) nickel precatalyst produced predominantly C 10 -dimers with nearly identical product distributions. The dimers produced by the nickel catalysts are less-branched than acid-catalyzed (e.g., BF 3 ) dimers, due to the ability of the nickel intermediate to function as both an olefin isomerization and a dimerization catalyst, whereby C−C bond formation occurs preferentially between a primary carbon of one olefin and the less substituted carbon of the inserting olefin. The dimerization of the regioisomers of 2-methyl-2-butene, 2-methyl-1-butene, and 3methyl-1-butene, utilizing the aforementioned nickel precatalysts, resulted in the same structural isomers of the dimers but different product distributions, indicating that dimerization occurred at similar rate or faster than isomerization. Stoichiometric experiments, product analysis, and observations from in situ nuclear magnetic resonance spectroscopy support a mechanism whereby a short-lived nickel-hydride intermediate promotes chain insertion, chain walking, and isomerization to give less-branched dimers from highly substituted olefins than would be achieved with acid-catalyzed dimerization.

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Nickel catalyzed dimerization reactions of vinylidene compounds: Head-to-head couplings and catalyst stabilization

Cited by 8 publications

References 14 publications

Effect of Sn on Isobutane Dehydrogenation Performance of Ni/SiO₂ Catalyst: Adsorption Modes and Adsorption Energies of Isobutane and Isobutene

Effect of Sn on Isobutane Dehydrogenation Performance of Ni/SiO₂ Catalyst: Adsorption Modes and Adsorption Energies of Isobutane and Isobutene

Nickel Catalyzed Olefin Oligomerization and Dimerization

Nickel-Catalyzed Dimerization of Di- and Trisubstituted Olefins

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Nickel catalyzed dimerization reactions of vinylidene compounds: Head-to-head couplings and catalyst stabilization

Cited by 8 publications

References 14 publications

Effect of Sn on Isobutane Dehydrogenation Performance of Ni/SiO2 Catalyst: Adsorption Modes and Adsorption Energies of Isobutane and Isobutene

Effect of Sn on Isobutane Dehydrogenation Performance of Ni/SiO2 Catalyst: Adsorption Modes and Adsorption Energies of Isobutane and Isobutene

Nickel Catalyzed Olefin Oligomerization and Dimerization

Nickel-Catalyzed Dimerization of Di- and Trisubstituted Olefins

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Product

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Effect of Sn on Isobutane Dehydrogenation Performance of Ni/SiO₂ Catalyst: Adsorption Modes and Adsorption Energies of Isobutane and Isobutene

Effect of Sn on Isobutane Dehydrogenation Performance of Ni/SiO₂ Catalyst: Adsorption Modes and Adsorption Energies of Isobutane and Isobutene