Heavy Metal with a Heavy Impact: Olefin Dimerization Reactions in Triphenylbismuth Buffered Chloroaluminate Ionic Liquids

Dötterl, Matthias; Alt, Helmut G.

doi:10.1002/cctc.201100182

Cited by 15 publications

(16 citation statements)

References 50 publications

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“…The catalytic results indicated that the mechanism of these homogeneous aluminum chloride‐based systems was similar to the mechanism we proposed for nickel‐catalyzed olefin dimerization reactions in buffered chloroaluminate ionic liquids 33. On contact with aluminum chloride, a nickel halide complex forms Ni(AlX 4 ) 2 (X=Cl, Br) species37 with weakly coordinating tetrahaloaluminate anions.…”

Section: Resultssupporting

confidence: 71%

“…Although strongly coordinating ligands, such as bidentate diimines or monodentate basic phosphines, remain at the active nickel center, the weakly coordinating [AlX 4 ] − anions can easily be replaced by olefins or buffer molecules. As no alkylating agent was present in these systems, we also assume that the catalytic cycle started with the formation of nickelacyclopentane 33…”

Section: Resultsmentioning

confidence: 99%

“…As no reactive alkylaluminum groups were present in such buffered chloroaluminate melts, simple amine hydrochlorides could be used instead of quaternary ammonium salts. This is a great advantage because depleted systems can be recycled simply by acid–base extraction 33…”

Section: Resultsmentioning

confidence: 99%

“…Biphasic nickel‐catalyzed olefin conversion reactions are limited by the mass transport of olefins and not by the catalyst above a certain catalyst concentration 28c. Thus, productivities, which are related to the total amount of the ionic liquid, were obtained instead of activities 33. As ethene polymerization reactions occurred at the surface of the ionic liquids, mixing became a problem with increasing polymer contents.…”

Section: Resultsmentioning

confidence: 99%

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Buffered Aluminum Chloride as a Highly Efficient Cocatalyst for Olefin Dimerization and Polymerization

Dötterl

Alt

2012

ChemCatChem

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A binary cocatalyst system based on simple aluminum chloride and weak Lewis bases such as triphenylbismuth or N‐methylpyrrole has been developed. A donor–acceptor interaction kept aluminum chloride dissolved in toluene or methylene chloride. The systems were investigated by use of 27Al NMR spectroscopy and were used as cocatalysts in nickel‐catalyzed dimerization and polymerization reactions of α‐olefins. Their Lewis acidities correlated to the line width of the 27Al NMR signals and were influenced by the solvent and the type and amount of buffer. For propene dimerization reactions, dimer selectivities of up to 95 % were achieved. Ethene was dimerized to give butenes (up to 92 %), of which 79 % were 1‐butene. With a Brookhart‐type nickel diimine complex, ethene was polymerized with a cocatalyst solely based on aluminum chloride. Up to 38 wt % of the reaction products were polyethylene with a typical molecular weight of 140 kg mol−1. The donor–acceptor interactions of triphenylbismuth and N‐methylpyrrole with aluminum chloride were successfully transferred to Lewis acidic chloroaluminate ionic liquids. Ethene was polymerized with a nickel diimine complex dissolved in buffered chloroaluminate ionic liquids in the absence of alkylaluminum groups.

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Section: Resultssupporting

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Buffered Aluminum Chloride as a Highly Efficient Cocatalyst for Olefin Dimerization and Polymerization

Dötterl

Alt

2012

ChemCatChem

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“…Conducting the oligomerization process of ethylene in biphasic systems allows for separating the catalyst easily from the obtained oligomer product and reusing it in recycling oligomerization processes . In addition to being used as solvents, the chloroaluminate‐type ionic liquids are also used as catalysts in the oligomerization process of ethylene …”

Section: Introductionmentioning

confidence: 99%

Oligomerization of ethylene in the presence of heterogenized complex catalytic systems based on ionic liquid‐type substituted zirconium phenolates

Khamiyev

Azizov

Khanmetov

et al. 2016

Applied Organom Chemis

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The oligomerization of ethylene was investigated in the presence of novel catalytic systems consisting of alkylaluminium chlorides and heterogenized zirconium phenolates containing amino and imino hydrochloride substituents. It was determined that the composition of a synthesized oligomer and the activity or selectivity of the catalyst systems depend on various parameters such as the molar ratio of Zr:Al, the composition of alkylaluminium, the temperature of the reaction, the pressure of ethylene and the structure of zirconium phenolates. The results showed that C 4 -C 10 linear α-olefins were obtained with high selectivity when diethylaluminium chloride was used as a co-catalyst. The process of the separation of a synthesized oligomer from the catalyst containing amino and imino hydrochloride ionic liquid substituents was carried out by simple decantation, and after this process zirconium complexes could be reused several times for successive ethylene oligomerizations.

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Nickel‐Catalyzed Propene Dimerization Reactions in Triphenylbismuth‐Buffered Chloroaluminate Ionic Liquids: High Performance with Unconventional Cations

Dötterl

Alt

2012

Adv Synth Catal

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The addition of triphenylbismuth (BiPh 3 ) efficiently buffers Lewis acidic chloroaluminate ionic liquids over a wide range of compositions. Since the melting points of these ternary mixtures are lower compared to unbuffered chloroaluminate systems, the scope of cations for the formation of buffered room temperature ionic liquids is greatly extended. The buffered ionic liquids were used to activate nickel complexes for selective biphasic propene dimerization reactions. Lifetimes, selectivities and productivities of such dimerization catalysts could be adjusted by the choice of the cation and the composition. At lower reaction temperatures, the selectivities to give dimers increased significantly. Propene dimers were obtained with selectivities of up to 98%. A cation screening with 100 ammonium and phosphonium halide salts was performed. N-Methylpyrrolidine hydrochloride gave the best results in terms of selectivity and lifetime. Propene dimerization reactions in BiPh 3 -buffered chloroaluminate melts were catalyzed by various soluble nickel compounds with similar performances. The introduction of basic, sterically demanding tricyclohexylphosphine ligands led to higher degrees of branching, however, at the expense of lower dimer selectivities.

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Heavy Metal with a Heavy Impact: Olefin Dimerization Reactions in Triphenylbismuth Buffered Chloroaluminate Ionic Liquids

Abstract: The Supporting Information for this article contains detailed experimental procedures, preparation of the ammonium salts, ionic liquids, and complex 1, as well as a catalyst concentration series, and is available on the WWW under http://dx.

Cited by 15 publications

References 50 publications

Buffered Aluminum Chloride as a Highly Efficient Cocatalyst for Olefin Dimerization and Polymerization

Buffered Aluminum Chloride as a Highly Efficient Cocatalyst for Olefin Dimerization and Polymerization

Oligomerization of ethylene in the presence of heterogenized complex catalytic systems based on ionic liquid‐type substituted zirconium phenolates

Nickel‐Catalyzed Propene Dimerization Reactions in Triphenylbismuth‐Buffered Chloroaluminate Ionic Liquids: High Performance with Unconventional Cations

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