A broadly tunable synthesis of linear α-olefins

Abstract

The catalytic synthesis of linear α-olefins from ethylene is a technologically highly important reaction. A synthesis concept allowing the formation of selective products and various linear α-olefin product distributions with one catalyst system is highly desirable. Here, we describe a trimetallic catalyst system (Y–Al–Ni) consisting of a rare earth metal polymerization catalyst which can mediate coordinative chain transfer to triethylaluminum combined with a simultaneously operating nickel β-hydride elimination/transfer catalyst. This nickel catalyst displaces the grown alkyl chains forming linear α-olefins and recycles the aluminum-based chain transfer agent. With one catalyst system, we can synthesize product spectra ranging from selective 1-butene formation to α-olefin distributions centered at 850 gmol−1 with a low polydispersity. The key to this highly flexible linear α-olefin synthesis is the easy tuning of the rates of the Y and Ni catalysis independently of each other. The reaction is substoichiometric or formally catalytic regarding the chain transfer agent.

Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts

“…Linear α-olefins, derived from light alkene oligomerization reactions, are broadly used as lubricants and co-monomers in polymer synthesis, and represent one of few examples for which homogeneous catalysts 1 are still employed in bulk chemical production. Transition-metal compounds selectively convert light alkenes into industrially-relevant products 2 , but their limited recyclability and excessive use of solvent and activators present environmental and economic limitations.…”

Ethylene Oligomerization over SiO2−Al2O3 Supported Ni2P Catalyst

“…These P atoms can be used to adjust the molecular weight and chain length of the produced α‐olefins . Along with the active Ni complex, a co‐catalyst is generally required, with examples including methylaluminoxane, Al(CH 3 ) 3 , NaBH 4 , and LiAlH 4 . Numerous studies regarding homogeneous oligomerization systems have proposed the Cossee‐Arlman mechanism involving the following steps: catalyst activation (generation of nickel hydride species), ethylene insertion and propagation, and termination (detachment of the oligomers from the catalyst) …”

“…[5] Along with the active Ni complex, a co-catalyst is generally required, with examples including methylaluminoxane, Al(CH 3 ) 3 , NaBH 4 , and LiAlH 4 . [3,4,6,9] Numerous studies regarding homogeneous oligomerization systems have proposed the Cossee-Arlman mechanism involving the following steps: catalyst activation (generation of nickel hydride species), ethylene insertion and propagation, and termination (detachment of the oligomers from the catalyst). [6,9,10] Heterogeneous catalysts have recently been applied for ethylene oligomerization due to efficient separation of oligomers from the catalyst system.…”

“…[3,4,6,9] Numerous studies regarding homogeneous oligomerization systems have proposed the Cossee-Arlman mechanism involving the following steps: catalyst activation (generation of nickel hydride species), ethylene insertion and propagation, and termination (detachment of the oligomers from the catalyst). [6,9,10] Heterogeneous catalysts have recently been applied for ethylene oligomerization due to efficient separation of oligomers from the catalyst system. [11][12][13][14] Reported catalysts typically consist of oxidized Ni species as an active centre and an Aldoped SiO 2 support (e. g., Al-SBA-15, Al-MCM-41, zeolite, and amorphous SiO 2 À Al 2 O 3 ).…”

Arabinogalactan Proteins Are the Possible Extracellular Molecules for Binding Exogenous Cerium(III) in the Acidic Environment Outside Plant Cells

“…Rare earth elements [REE(III)] are comprised of the lanthanide elements (atomic number 57 to 71) together with scandium (atomic number is 21) and yttrium (atomic number is 39) in the periodic table of elements (Redling, 2006). With the ever-increasing update of the knowledge about the specific properties of REE(III) in physics, chemistry and biology, the applications of REE(III) are unprecedentedly increased in the field of energy (Bae et al, 2017; Tou et al, 2017), materials (Adesina et al, 2017; Hammond et al, 2017; Zhong et al, 2017), catalysis (Kim et al, 2016; Gollwitzer et al, 2017), biology (Aciego et al, 2017), environment (Aciego et al, 2017), etc., As a result of these applications, REE(III) have been released and widely accumulated in global environment in a large quantity (Shaltout et al, 2013; Hao et al, 2016; Paye et al, 2016). REE(III) accumulated in the environment inevitably makes contact with plants in the ecosystem.…”