Academic Journal
Computer-aided kinetic network modeling of orthoester metathesis.
| Τίτλος: | Computer-aided kinetic network modeling of orthoester metathesis. |
|---|---|
| Συγγραφείς: | Muzyka, Claire, Silva Brenes, Diana Vanessa, Monbaliu, Jean-Christophe |
| Συνεισφορές: | Center for Integrated Technology and Organic Synthesis, MolSys - Molecular Systems - ULiège |
| Πηγή: | Physical Chemistry Chemical Physics, 28 (22), 13488 - 13495 (2026-06-10) |
| Στοιχεία εκδότη: | Royal Society of Chemistry, 2026. |
| Έτος έκδοσης: | 2026 |
| Θεματικοί όροι: | DFT calculation, Exchange reaction, Integrated workflow, Kinetic models, Network models, Spectral decomposition, Physical, chemical, mathematical & earth Sciences, Chemistry, Physique, chimie, mathématiques & sciences de la terre, Chimie |
| Περιγραφή: | Dynamic covalent exchange (DCE) reactions often generate complex mixtures that make quantitative analysis challenging despite involving mechanistically simple individual processes. Here we introduce an integrated workflow combining automated spectral decomposition, mechanistically guided kinetic modeling, and targeted DFT calculations to elucidate the DCE between triethyl orthoformate and ethylene glycol. Tensor-based analysis of time-resolved 1H NMR data identified ten distinct species, which were incorporated into a refined kinetic model providing excellent agreement with experiments (R2 > 0.95) and strong predictive performance under various conditions (R2 > 0.90). DFT calculations focused on the acid-promoted activation step supported the kinetic parameters and clarified how substrate structure, catalyst identity, solvent, and released alcohols influence activation barriers and catalyst availability. Together, these results deliver a coherent description of the reaction network and establish a generalizable strategy for analyzing and tuning complex dynamic covalent systems. |
| Τύπος εγγράφου: | journal article http://purl.org/coar/resource_type/c_6501 article peer reviewed |
| Γλώσσα: | English |
| Relation: | http://pubs.rsc.org/en/content/articlepdf/2026/CP/D6CP00391E; urn:issn:1463-9076; urn:issn:1463-9084 |
| DOI: | 10.1039/d6cp00391e |
| Σύνδεσμος πρόσβασης: | https://orbi.uliege.be/handle/2268/346784 |
| Rights: | open access http://purl.org/coar/access_right/c_abf2 info:eu-repo/semantics/openAccess |
| Αριθμός Καταχώρησης: | edsorb.346784 |
| Βάση Δεδομένων: | ORBi |
| FullText | Text: Availability: 0 CustomLinks: – Url: https://orbi.uliege.be/handle/2268/346784# Name: EDS - ORBi (ns324271) Category: fullText Text: View record at ORBi |
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| Header | DbId: edsorb DbLabel: ORBi An: edsorb.346784 RelevancyScore: 1038 AccessLevel: 3 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 1037.62463378906 |
| IllustrationInfo | |
| Items | – Name: Title Label: Title Group: Ti Data: Computer-aided kinetic network modeling of orthoester metathesis. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Muzyka%2C+Claire%22">Muzyka, Claire</searchLink><br /><searchLink fieldCode="AR" term="%22Silva+Brenes%2C+Diana+Vanessa%22">Silva Brenes, Diana Vanessa</searchLink><br /><searchLink fieldCode="AR" term="%22Monbaliu%2C+Jean-Christophe%22">Monbaliu, Jean-Christophe</searchLink> – Name: Author Label: Contributors Group: Au Data: Center for Integrated Technology and Organic Synthesis<br />MolSys - Molecular Systems - ULiège – Name: TitleSource Label: Source Group: Src Data: Physical Chemistry Chemical Physics, 28 (22), 13488 - 13495 (2026-06-10) – Name: Publisher Label: Publisher Information Group: PubInfo Data: Royal Society of Chemistry, 2026. – Name: DatePubCY Label: Publication Year Group: Date Data: 2026 – Name: Subject Label: Subject Terms Group: Su Data: <searchLink fieldCode="DE" term="%22DFT+calculation%22">DFT calculation</searchLink><br /><searchLink fieldCode="DE" term="%22Exchange+reaction%22">Exchange reaction</searchLink><br /><searchLink fieldCode="DE" term="%22Integrated+workflow%22">Integrated workflow</searchLink><br /><searchLink fieldCode="DE" term="%22Kinetic+models%22">Kinetic models</searchLink><br /><searchLink fieldCode="DE" term="%22Network+models%22">Network models</searchLink><br /><searchLink fieldCode="DE" term="%22Spectral+decomposition%22">Spectral decomposition</searchLink><br /><searchLink fieldCode="DE" term="%22Physical%2C+chemical%2C+mathematical+%26+earth+Sciences%22">Physical, chemical, mathematical & earth Sciences</searchLink><br /><searchLink fieldCode="DE" term="%22Chemistry%22">Chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Physique%2C+chimie%2C+mathématiques+%26+sciences+de+la+terre%22">Physique, chimie, mathématiques & sciences de la terre</searchLink><br /><searchLink fieldCode="DE" term="%22Chimie%22">Chimie</searchLink> – Name: Abstract Label: Description Group: Ab Data: Dynamic covalent exchange (DCE) reactions often generate complex mixtures that make quantitative analysis challenging despite involving mechanistically simple individual processes. Here we introduce an integrated workflow combining automated spectral decomposition, mechanistically guided kinetic modeling, and targeted DFT calculations to elucidate the DCE between triethyl orthoformate and ethylene glycol. Tensor-based analysis of time-resolved 1H NMR data identified ten distinct species, which were incorporated into a refined kinetic model providing excellent agreement with experiments (R2 > 0.95) and strong predictive performance under various conditions (R2 > 0.90). DFT calculations focused on the acid-promoted activation step supported the kinetic parameters and clarified how substrate structure, catalyst identity, solvent, and released alcohols influence activation barriers and catalyst availability. Together, these results deliver a coherent description of the reaction network and establish a generalizable strategy for analyzing and tuning complex dynamic covalent systems. – Name: TypeDocument Label: Document Type Group: TypDoc Data: journal article<br />http://purl.org/coar/resource_type/c_6501<br />article<br />peer reviewed – Name: Language Label: Language Group: Lang Data: English – Name: NoteTitleSource Label: Relation Group: SrcInfo Data: http://pubs.rsc.org/en/content/articlepdf/2026/CP/D6CP00391E; urn:issn:1463-9076; urn:issn:1463-9084 – Name: DOI Label: DOI Group: ID Data: 10.1039/d6cp00391e – Name: URL Label: Access URL Group: URL Data: <link linkTarget="URL" linkTerm="https://orbi.uliege.be/handle/2268/346784" linkWindow="_blank">https://orbi.uliege.be/handle/2268/346784</link> – Name: Copyright Label: Rights Group: Cpyrght Data: open access<br />http://purl.org/coar/access_right/c_abf2<br />info:eu-repo/semantics/openAccess – Name: AN Label: Accession Number Group: ID Data: edsorb.346784 |
| PLink | https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=edsorb&AN=edsorb.346784 |
| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1039/d6cp00391e Languages: – Text: English Subjects: – SubjectFull: DFT calculation Type: general – SubjectFull: Exchange reaction Type: general – SubjectFull: Integrated workflow Type: general – SubjectFull: Kinetic models Type: general – SubjectFull: Network models Type: general – SubjectFull: Spectral decomposition Type: general – SubjectFull: Physical, chemical, mathematical & earth Sciences Type: general – SubjectFull: Chemistry Type: general – SubjectFull: Physique, chimie, mathématiques & sciences de la terre Type: general – SubjectFull: Chimie Type: general Titles: – TitleFull: Computer-aided kinetic network modeling of orthoester metathesis. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Muzyka, Claire – PersonEntity: Name: NameFull: Silva Brenes, Diana Vanessa – PersonEntity: Name: NameFull: Monbaliu, Jean-Christophe – PersonEntity: Name: NameFull: Center for Integrated Technology and Organic Synthesis – PersonEntity: Name: NameFull: MolSys - Molecular Systems - ULiège IsPartOfRelationships: – BibEntity: Dates: – D: 10 M: 06 Type: published Y: 2026 |
| ResultId | 1 |