Molecular structure, magnetic properties and catalytic activity in selective ethylene dimerization of nickel (II) complexes with bis(3,5-dimethylpyrazol-1-yl)methane

Zubkevich, Sergey V.; Тuskaev, Vladislav А.; Гагиева, С. Ч.; Павлов, А. А.; Khrustalev, Victor N.; Kurmaev, Dmitrii A.; Kolosov, N.A.; Булычев, Б. М.

doi:10.1016/j.molstruc.2020.127692

Cited by 11 publications

(22 citation statements)

References 81 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is known, that the closer is the nucleus to the paramagnetic metal the faster is the relaxation and, thus, the width of the signal increases. The proposed annotations are consistent with those of similar complexes for which the DFT calculations have been performed [56]. Complexes without substituents near to the donor nitrogen atom (1, 2, 10, 11) are insoluble in common organic solvents except alcohols.…”

Section: Synthesis and Characterizationsupporting

confidence: 85%

“…c determined using GC; C4 = , C6 =total shares of each oligomer fraction; α-C4 = , α-C6 = -shares of α-isomer in each fraction. d reported in [56,57], used for comparison of the results e trace amounts of octenes (< 1%) are present in the mixture All complexes except 2 exhibited catalytic activities higher than 1000 kgoligomer•mol[Ni] −1 •h −1 that exceed the activity of previously reported parent complex 3. The lowest activity of 2 is attributed to the low solubility of compound in reaction media (toluene) in the absence of substituents in pyrazole rings.…”

Section: Ethylene Oligomerization and Friedel-crafts Alkylation Of Tomentioning

confidence: 86%

“…Synthesis of complex 3 was previously reported by us in [56]. All other nickel(II) dibromide complexes have been prepared by interaction of Ni(DME)Br2 with corresponding ligand in THF (1, 4-11) or CH3CN (2) (Scheme 2).…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“…Complexes 1,2,4-11 were activated either with Et2AlCl or Et3Al2Cl3 and evaluated for their ability to catalyze ethylene oligomerization ( Table 2). Precatalyst 3, previously described by us in [56,57], was introduced for proper comparison of the results.…”

Section: Ethylene Oligomerization and Friedel-crafts Alkylation Of Tomentioning

confidence: 99%

“…Nickel(II) halide complexes with bis(3,5-dimethylpyrazol-1-yl)methane have been earlier described by Reedjik and coworkers [73][74][75]. Recently we have reported catalytic studies of bis(3,5-dimethylpyrazol-1-yl)methane nickel(II) bromide in ethylene oligomerization [56,57]. Oligomerization of ethylene yielding C4-C20 branched olefins catalyzed by substituted bis(pyrazolyl)methane nickel complexes was also reported by Fumiyuki [76].…”

Section: Introductionmentioning

confidence: 97%

See 4 more Smart Citations

Trapping the Short-Chain Odd Carbon Number Olefins Using Nickel(II)-catalyzed Tandem Ethylene Oligomerization and Friedel-Crafts Alkylation of Toluene

Zubkevich¹,

Тuskaev²,

Гагиева³

et al. 2020

Preprint

Self Cite

View full text Add to dashboard Cite

<div>Nickel(II) complexes with pyrazole-based ligands are widely employed in catalysis of ethylene</div><div>oligomerization and subsequent Friedel-Crafts alkylation of toluene. We have prepared ten new</div><div>nickel(II) dibromide complexes with various substituted bis(azolyl)methanes. They have been</div><div>characterized using <sup>1</sup>H NMR, IR, MALDI-TOF and elemental analysis. The structures of three</div><div>complexes have been unambiguously established using X-ray diffraction. It was found that these</div><div>complexes in the presence of Et<sub>2</sub>AlCl or Et<sub>3</sub>Al<sub>2</sub>Cl<sub>3</sub> are active both in ethylene oligomerization and</div><div>Friedel-Crafts alkylation processes (activity up to 3720 kgoligomer·mol[Ni]<sup>−1</sup>·h<sup>−1</sup>). The use of Et<sub>3</sub>Al<sub>2</sub>Cl<sub>3</sub></div><div>results in the higher share of alkylated products (up to 60%). Moreover, catalytic systems activated with</div><div>Et<sub>3</sub>Al<sub>2</sub>Cl<sub>3</sub> produced small amounts of odd carbon number olefins (up to 0.8%). The Friedel-Crafts</div><div>alkylation was used as a trap for previously undetected short-chain odd carbon number olefins (C<sub>3</sub> and</div><div>C<sub>5</sub>).</div>

show abstract

Section: Synthesis and Characterizationsupporting

confidence: 85%

Section: Ethylene Oligomerization and Friedel-crafts Alkylation Of Tomentioning

confidence: 86%

Section: Synthesis and Characterizationmentioning

confidence: 99%

Section: Ethylene Oligomerization and Friedel-crafts Alkylation Of Tomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

See 3 more Smart Citations

Trapping the Short-Chain Odd Carbon Number Olefins Using Nickel(II)-catalyzed Tandem Ethylene Oligomerization and Friedel-Crafts Alkylation of Toluene

Zubkevich¹,

Тuskaev²,

Гагиева³

et al. 2020

Preprint

Self Cite

View full text Add to dashboard Cite

show abstract

Catalytic behavior tuning via structural modifications of silylated‐diphosphine Ni(II) complexes for ethylene selective dimerization

Wang

Alam

Chang

et al. 2020

Applied Organom Chemis

View full text Add to dashboard Cite

The methylene spacers and an uncoordinated diphenylphosphine moiety in the scaffold of the CH 3 Si(CH 2) n (PPh 2) 3 and Si(CH 2 PPh 2) 4-type silylated diphosphine Ni(II) complex systems have a marked impact on their catalytic performance in selective ethylene dimerization. Ni(II)-based precatalyst 1, bearing two methylene spacers in its framework, exhibited the highest catalytic activity of 1.29 × 10 8 g (mol Ni)-1 h-1 , while precatalyst 3, with three methylene spacers, affords the highest product selectivity (88%) toward the C 4 fraction. Crystallographic investigations revealed that the precatalyst 3 adopts the mononuclear bidentate binding mode and the steric constraints of its uncoordinated diphenylphosphine moiety may successfully tailor the catalytic environment of the catalyst. The precatalyst 4 may form a dinuclear complex and exhibits high catalytic activity by changing the ligand/Ni molar ratio. The high C 4 selectivity of precatalyst 3 has been rationalized by density functional theory (DFT) calculations and found to be consistent with the experimental results. The study also revealed that designing new systems of Ni(II)-based complexes and their systematic modifications may further provide potential and industrially viable catalyst systems for selective ethylene oligomerization.

show abstract

Trapping the Short‐Chain Odd Carbon Number Olefins Using Nickel(II)‐Catalyzed Tandem Ethylene Oligomerization and Friedel‐Crafts Alkylation of Toluene

et al. 2023

Self Cite

View full text Add to dashboard Cite

Comprehensive SummaryNickel(II) complexes with pyrazole‐based ligands are widely employed in catalysis of ethylene oligomerization and subsequent Friedel‐Crafts alkylation of toluene. We have prepared ten new nickel(II) dibromide complexes with various substituted bis(azolyl)methanes. They have been characterized using 1H NMR, IR, high resolution mass spectrometry and elemental analysis. The structures of three complexes have been unambiguously established using X‐ray diffraction. It was found that these complexes in the presence of Et2AlCl or Et3Al2Cl3 are active both in ethylene oligomerization and Friedel‐Crafts alkylation processes (activity up to 3720 kgoligomer·mol[Ni]−1·h−1). The use of Et3Al2Cl3 results in a higher share of alkylated products (up to 60%). Moreover, catalytic systems activated with Et3Al2Cl3 produced small amounts of odd carbon number olefins (up to 0.8%). The Friedel‐Crafts alkylation was used as a trap for previously undetected short‐chain odd carbon number olefins (C3 and C5).

show abstract

Molecular structure, magnetic properties and catalytic activity in selective ethylene dimerization of nickel (II) complexes with bis(3,5-dimethylpyrazol-1-yl)methane

Cited by 11 publications

References 81 publications

Trapping the Short-Chain Odd Carbon Number Olefins Using Nickel(II)-catalyzed Tandem Ethylene Oligomerization and Friedel-Crafts Alkylation of Toluene

Trapping the Short-Chain Odd Carbon Number Olefins Using Nickel(II)-catalyzed Tandem Ethylene Oligomerization and Friedel-Crafts Alkylation of Toluene

Catalytic behavior tuning via structural modifications of silylated‐diphosphine Ni(II) complexes for ethylene selective dimerization

Trapping the Short‐Chain Odd Carbon Number Olefins Using Nickel(II)‐Catalyzed Tandem Ethylene Oligomerization and Friedel‐Crafts Alkylation of Toluene

Contact Info

Product

Resources

About