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Record W2315258591 · doi:10.1021/om501013m

Effect of Cocatalysts and Solvent on Selective Ethylene Oligomerization

2015· article· en· W2315258591 on OpenAlexaff
Shaneesh Vadake Kulangara, Daniël Haveman, Bala Vidjayacoumar, Ilia Korobkov, Sandro Gambarotta, R. Duchateau

Bibliographic record

VenueOrganometallics · 2015
Typearticle
Languageen
FieldChemistry
TopicOrganometallic Complex Synthesis and Catalysis
Canadian institutionsUniversity of Ottawa
Fundersnot available
KeywordsChemistryEthyleneMethylcyclohexaneMethylaluminoxaneCatalysisSelectivityChromiumPolymer chemistryLigand (biochemistry)Solvent1-HexeneMedicinal chemistryOrganic chemistryPolymerMetallocenePolymerization

Abstract

fetched live from OpenAlex

Ethylene oligomerization activities of chromium catalysts stabilized by different dipyrrole-based ancillary ligands, [(Ph 2 C(C 4 H 4 N) 2 )] ( 2 ), [Ph 2 C(C 4 H 4 N)(C 5 H 6 N)] ( 3 ), [(Et) 2 C(C 4 H 4 N) 2 ] ( 4 ), and [(C 6 H 5 )(C 5 H 4 N)C(C 4 H 4 N)(C 5 H 6 N)] ( 5 ), have been investigated using different activation methods, and the results have been compared with the commercial Chevron–Phillips ethylene trimerization system. Upon activation with triethylaluminum (TEA), chromium catalysts stabilized by dipyrrole-based ligands 2 – 5 showed a lower activity and selectivity compared to the Chevron–Phillips trimerization system based on 2,5-dimethylpyrrole ( 1 ) as the ancillary ligand. However, unprecedented increases in both activity and selectivity have been observed by carrying out the oligomerization in methylcyclohexane using depleted-methylaluminoxane (DMAO) along with triisobutylaluminum (TIBA) (1:2 ratio) as cocatalyst system under mild conditions, even for the Chevron–Phillips system itself. Well-defined chromium complexes, [(Ph 2 C(C 4 H 3 N) 2 )Cr(Cl)(THF) 3 ] ( 6 ) and {[Ph 2 C(C 4 H 3 N)(C 5 H 6 N]Cr(THF)(μ-Cl)} 2 ( 7 ), have been synthesized and fully characterized. Upon activating with MAO, catalyst 7 produced a statistical distribution of oligomers, whereas under identical oligomerization conditions catalyst 6/ MAO was found to be inactive. The use of MeAlCl 2 as cocatalyst to activate 7 resulted in the switching of the catalyst’s behavior from producing a statistical distribution of LAOs to the selective trimerization of ethylene to 1-hexene. The addition of dialkylzinc along with MAO resulted in an unprecedented activity increase.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesInsufficient payload (model declined to judge)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.089
Threshold uncertainty score0.999

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0010.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.013
GPT teacher head0.244
Teacher spread0.231 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

Study designBench or experimental
Domainnot available
GenreEmpirical

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations39
Published2015
Admission routes1
Has abstractyes

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