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Record W4389305925 · doi:10.1021/acscatal.3c04918

Rethinking the Lewis Acidity of Cationic Gallium and Indium Catalysts

2023· article· en· W4389305925 on OpenAlexafffund
Chatura Goonesinghe, Hyuk‐Joon Jung, Isaiah O. Betinol, Joshua R. Gaffen, Charley N. Garrard, Joseph Chang, Kimia Hosseini, Hootan Roshandel, Kudzanai Nyamayaro, Brian O. Patrick, Maria B. Ezhova, Christopher B. Caputo, Thomas Baumgartner, Jolene P. Reid, Parisa Mehrkhodavandi

Bibliographic record

VenueACS Catalysis · 2023
Typearticle
Languageen
FieldChemical Engineering
TopicCarbon dioxide utilization in catalysis
Canadian institutionsYork UniversityUniversity of British Columbia
FundersNatural Sciences and Engineering Research Council of CanadaUniversity of British ColumbiaCanada Research Chairs
KeywordsGalliumIndiumLewis acids and basesCationic polymerizationChemistryReactivity (psychology)CatalysisAdductElectrophilePolymer chemistryOrganic chemistry

Abstract

fetched live from OpenAlex

Indium compounds are commonly considered weaker Lewis acids than their gallium counterparts. We explore the difference in Lewis acidity of the cationic dialkylgallium [GaR 2 (THF) 2 ] + and indium [InR 2 (THF) n ] + species and show that the gallium compounds are more active for the cationic polymerization of epoxide and ε-caprolactone. We rationalize this difference in reactivity by quantifying the relative Lewis acidity of the gallium and indium complexes. Experimental probes such as the Gutmann–Beckett and the fluorescent Lewis adduct method show that the gallium complexes are somewhat more Lewis acidic than the indium analogues, but not sufficiently to explain the major difference in reactivity. Computational studies suggest that, in solution, indium complexes exist in an equilibrium between [InR 2 (THF) 2 ] + and [InR 2 (THF) 3 ] + while the gallium species are stable as [GaR 2 (THF) 2 ] + . Global Electrophilicity Index calculations for all possible THF coordinate compounds of alkylgallium and alkylindium show that indium species are consistently more Lewis acidic than their gallium counterparts with the same number of coordinated THF molecules. We propose that the slow reactivity of indium species is not due to weaker Lewis acidity but rather is due to their ability to accommodate additional donor substrates.

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)0.001
metaresearch head score (Gemma)0.001
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
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 score0.067
Threshold uncertainty score0.643

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0010.001
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.002
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

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 head0.022
GPT teacher head0.246
Teacher spread0.224 · 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.

The models applied no category: nothing in the taxonomy fit this work.
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

Citations13
Published2023
Admission routes2
Has abstractyes

Explore more

Same venueACS CatalysisSame topicCarbon dioxide utilization in catalysisFrench-language works237,207