Ionic Liquids and Catalysis: the<scp>IFP</scp>Biphasic Difasol Process

Olivier‐Bourbigou, Hélène; Favre, Frédéric; Forestière, A.; Hugues, F.

doi:10.1002/9783527628698.hgc005

Cited by 28 publications

(40 citation statements)

References 40 publications

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“…30,31 The new ligands 3 and 7 were prepared by conventional condensation of phenylene diamine with N-alkyl iminodiacetic acid diethylester (see Experimental Section). 3 ] which was characterised by NMR and X-ray diffraction (see Figure 5). …”

Section: Ligand and Complex Synthesismentioning

confidence: 99%

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Alternating α-Olefin Distributions via Single and Double Insertions in Chromium-Catalyzed Ethylene Oligomerization

et al. 2016

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The catalytic oligomerization of ethylene with chromium-based complexes containing bis(benzimidazolemethyl)amine (BIMA) ligands results in alternating distributions of linear α-olefins (LAOs). Extremely high activities are obtained (>100 000 g mmol–1 h–1 bar–1) with N-alkyl-substituted BIMA ligands, whereas bulky groups on the central nitrogen or alternative central donors result in much lower activities. Variations in the ligand backbone, as well as methylation of the benzimidazole units, lead to reduction in activity. The alternating LAO distributions have been mathematically analyzed using second-order recurrence relations. The shape of the distributions is affected by ethylene pressure (1–4 bar) and by the cocatalyst to some degree. On the basis of the results and analysis presented herein, we propose that the alternating behavior originates from the ability of these chromium BIMA catalysts to undergo single as well as double ethylene insertion reactions. A minor second distribution (<5 wt %) of 2-ethyl-1-alkenes is obtained under certain conditions, resulting from incorporation of 1-butene. DFT studies (M06L) and experimental observations regarding the reaction between AlMe3 and the N-methyl BIMA ligand 2 have shown that deprotonation of the benzimidazole N–H units can occur, which suggests a change in coordination of the BIMA ligand under oligomerization conditions.

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Section: Ligand and Complex Synthesismentioning

confidence: 99%

“…[1][2][3][4] Several commercial processes produce LAOs with different distributions of chain lengths.…”

Section: Introductionmentioning

confidence: 99%

Alternating α-Olefin Distributions via Single and Double Insertions in Chromium-Catalyzed Ethylene Oligomerization

et al. 2016

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“…Currently, 35 licensed DIMERSOL units with typical capacities between 20,000 and 90,000 tons per year are in use for selective dimerization reactions of short chain olefins. [4] About 30 years ago, Wilkes et al and Osteryoung et al reported the first room temperature ionic liquids based on aluminum chloride. [5] In the 1980s, these chloroaluminate ionic liquids were thoroughly investigated in terms of their physical and electrochemical properties.…”

Section: Introductionmentioning

confidence: 99%

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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“…In this respect, the sterics of the bis(trimethylsilylamide) ligand promote mononuclear 3-coordinate structures (9)(10)(11)(12). Mesitylanilido-and triphenylsilyloxo-chlorido species 16 and 18, respectively, dimerize via chlorido bridge formation, while the 3-coordinate DiPPanilido-chlorido derivative 13, that was prepared under carefully controlled conditions in octane, easily conproportionates in polar solvents by ligand redistribution to form the thermodynamically more stable mononuclear 3-coordinate bis(anilido) species 14 and 15.…”

Section: N1 Fe1 Cl1mentioning

confidence: 99%

“…Ethylene, propylene and butenes are in increasing demand [3][4][5][6][7][8][9][10][11][12][13]. Ethylene alone is at the origin of ca.…”

Section: Introductionmentioning

confidence: 99%

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Danopoulos

Braunstein

2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Dedicated to the memory of Yves Chauvin, a most remarkable and visionary man and scientist, with gratitude for our scientific and non-scientific conversations and a very fruitful and enjoyable collaboration.Abstract -Two major aspects of coordination/organometallic chemistry are discussed in this article: (i) the use of functional chelating ligands to stabilize metal complexes while allowing easy stereodifferentiation within the coordination sphere and (ii) the choice of suitable ligands to stabilize challenging 'underligated' metal complexes with electronically highly unsaturated metal centres, thus potentially displaying unusual reactivity. In both cases, the relevance to homogeneous catalysis will be discussed.Résumé -Contrôle de la sphère de coordination des métaux par les ligands : structures, réacti-vité et catalyse -Deux aspects majeurs de la chimie de coordination/organométallique sont discutés dans cet article : d'une part, l'utilisation de ligands chélatants fonctionnels pour stabiliser des complexes métalliques en permettant une différenciation stéréoélectronique aisée au sein de la sphère de coordination et, d'autre part, la sélection de ligands adaptés à la stabilisation de complexes métalliques sous-coordinés dont les centres métalliques sont hautement insaturés électroniquement et donc potentiellement le siège d'une réactivité inhabituelle. Dans les deux cas, nous évoquerons la pertinence de ces approches en catalyse homogène.

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Ionic Liquids and Catalysis: theIFPBiphasic Difasol Process

Cited by 28 publications

References 40 publications

Alternating α-Olefin Distributions via Single and Double Insertions in Chromium-Catalyzed Ethylene Oligomerization

Alternating α-Olefin Distributions via Single and Double Insertions in Chromium-Catalyzed Ethylene Oligomerization

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

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

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