Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFT
A mechanistic study investigating reactivity differences in metallocene-mediated cationic ring-opening homo- and copolymerization (CROP) of 2-<i>R</i>-oxazolines (R = Me, Ph) and ε-caprolactone (CL) is reported. Using density functional theory at the M06-2X level, we examined sequential...
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2025
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| _version_ | 1852015855390425088 |
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| author | Wijitra Jitonnom (22410515) |
| author2 | Tanchanok Wanjai (10280705) Mikko Linnolahti (1561828) Jitrayut Jitonnom (1811332) |
| author2_role | author author author |
| author_facet | Wijitra Jitonnom (22410515) Tanchanok Wanjai (10280705) Mikko Linnolahti (1561828) Jitrayut Jitonnom (1811332) |
| author_role | author |
| dc.creator.none.fl_str_mv | Wijitra Jitonnom (22410515) Tanchanok Wanjai (10280705) Mikko Linnolahti (1561828) Jitrayut Jitonnom (1811332) |
| dc.date.none.fl_str_mv | 2025-10-10T17:39:07Z |
| dc.identifier.none.fl_str_mv | 10.1021/acs.organomet.5c00116.s002 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/dataset/Origin_of_Comonomer_Reactivity_in_Zirconocene-Mediated_Polymerization_of_2_Oxazoline_and_Caprolactone_Insights_from_DFT/29821634 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biophysics Biochemistry Molecular Biology Evolutionary Biology Infectious Diseases Plant Biology Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified sequence preference stems phox initiation promotes gibbs activation energies electron density distributions defined block copolymers consecutive phox insertions bond insertion mechanisms 2 ‑ oxazoline rapid ring opening clear reactivity trend phoxcomeox </ b phoxcocl </ b meoxcophox </ b clcophox </ b clcomeox </ b mediated cationic ring 3 </ sub 2 </ sup monomer electronic structure 6 </ sub ε ‑ caprolactone 2 -< (< b opening homo comonomer reactivity >< sup r </ mediated polymerization theoretical foundation structural parameters reaction intermediates experimental observations enhanced zr designing well cp bonding controlled architectures cocatalyst system c – atomic charges >- oxazolines 2x level |
| dc.title.none.fl_str_mv | Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFT |
| dc.type.none.fl_str_mv | Dataset info:eu-repo/semantics/publishedVersion dataset |
| description | A mechanistic study investigating reactivity differences in metallocene-mediated cationic ring-opening homo- and copolymerization (CROP) of 2-<i>R</i>-oxazolines (R = Me, Ph) and ε-caprolactone (CL) is reported. Using density functional theory at the M06-2X level, we examined sequential monomer addition pathways, focusing on the C–O bond insertion mechanisms. Gibbs activation energies reveal a clear reactivity trend: <b>CLcoMeOX</b> < <b>PhOXcoMeOX</b> < <b>CLcoPhOX</b> < (<b>PhOX)</b><sub><b>2</b></sub> ≈ <b>(MeOX)</b><sub><b>2</b></sub> < <b>MeOXcoPhOX</b> ≈ <b>PhOXcoCL</b> < <b>MeOXcoCL</b>, aligning with experimental observations. This sequence preference stems from the interplay between the monomer electronic structure and catalyst–cocatalyst interactions. PhOX initiation promotes a rapid ring opening through enhanced Zr-Cp bonding and cation−π interactions, while consecutive PhOX insertions are hindered by π–π stacking effects. Initial CL insertion shows optimal reactivity with short Zr–B distances and extensive catalyst–cocatalyst contact areas, whereas reverse sequences face prohibitively high barriers. The [Ph<sub>3</sub>C]<sup>+</sup>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>]<sup>−</sup> cocatalyst system in acetonitrile provides optimal stabilization of reaction intermediates. Structure–property analysis reveals strong correlations (<i>R</i><sup>2</sup> > 0.6) between Gibbs activation energies and electronic and structural parameters, including Zr–B distances, atomic charges, and electron density distributions. These insights provide specific guidelines for optimizing metallocene-mediated CROP and offer a theoretical foundation for designing well-defined block copolymers with controlled architectures. |
| eu_rights_str_mv | openAccess |
| id | Manara_0f3ff4232ca2993261d8d09e83c9536d |
| identifier_str_mv | 10.1021/acs.organomet.5c00116.s002 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/29821634 |
| publishDate | 2025 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY-NC 4.0 |
| spelling | Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFTWijitra Jitonnom (22410515)Tanchanok Wanjai (10280705)Mikko Linnolahti (1561828)Jitrayut Jitonnom (1811332)BiophysicsBiochemistryMolecular BiologyEvolutionary BiologyInfectious DiseasesPlant BiologyChemical Sciences not elsewhere classifiedPhysical Sciences not elsewhere classifiedsequence preference stemsphox initiation promotesgibbs activation energieselectron density distributionsdefined block copolymersconsecutive phox insertionsbond insertion mechanisms2 ‑ oxazolinerapid ring openingclear reactivity trendphoxcomeox </ bphoxcocl </ bmeoxcophox </ bclcophox </ bclcomeox </ bmediated cationic ring3 </ sub2 </ supmonomer electronic structure6 </ subε ‑ caprolactone2 -<(< bopening homocomonomer reactivity>< supr </mediated polymerizationtheoretical foundationstructural parametersreaction intermediatesexperimental observationsenhanced zrdesigning wellcp bondingcontrolled architecturescocatalyst systemc –atomic charges>- oxazolines2x levelA mechanistic study investigating reactivity differences in metallocene-mediated cationic ring-opening homo- and copolymerization (CROP) of 2-<i>R</i>-oxazolines (R = Me, Ph) and ε-caprolactone (CL) is reported. Using density functional theory at the M06-2X level, we examined sequential monomer addition pathways, focusing on the C–O bond insertion mechanisms. Gibbs activation energies reveal a clear reactivity trend: <b>CLcoMeOX</b> < <b>PhOXcoMeOX</b> < <b>CLcoPhOX</b> < (<b>PhOX)</b><sub><b>2</b></sub> ≈ <b>(MeOX)</b><sub><b>2</b></sub> < <b>MeOXcoPhOX</b> ≈ <b>PhOXcoCL</b> < <b>MeOXcoCL</b>, aligning with experimental observations. This sequence preference stems from the interplay between the monomer electronic structure and catalyst–cocatalyst interactions. PhOX initiation promotes a rapid ring opening through enhanced Zr-Cp bonding and cation−π interactions, while consecutive PhOX insertions are hindered by π–π stacking effects. Initial CL insertion shows optimal reactivity with short Zr–B distances and extensive catalyst–cocatalyst contact areas, whereas reverse sequences face prohibitively high barriers. The [Ph<sub>3</sub>C]<sup>+</sup>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>]<sup>−</sup> cocatalyst system in acetonitrile provides optimal stabilization of reaction intermediates. Structure–property analysis reveals strong correlations (<i>R</i><sup>2</sup> > 0.6) between Gibbs activation energies and electronic and structural parameters, including Zr–B distances, atomic charges, and electron density distributions. These insights provide specific guidelines for optimizing metallocene-mediated CROP and offer a theoretical foundation for designing well-defined block copolymers with controlled architectures.2025-10-10T17:39:07ZDatasetinfo:eu-repo/semantics/publishedVersiondataset10.1021/acs.organomet.5c00116.s002https://figshare.com/articles/dataset/Origin_of_Comonomer_Reactivity_in_Zirconocene-Mediated_Polymerization_of_2_Oxazoline_and_Caprolactone_Insights_from_DFT/29821634CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/298216342025-10-10T17:39:07Z |
| spellingShingle | Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFT Wijitra Jitonnom (22410515) Biophysics Biochemistry Molecular Biology Evolutionary Biology Infectious Diseases Plant Biology Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified sequence preference stems phox initiation promotes gibbs activation energies electron density distributions defined block copolymers consecutive phox insertions bond insertion mechanisms 2 ‑ oxazoline rapid ring opening clear reactivity trend phoxcomeox </ b phoxcocl </ b meoxcophox </ b clcophox </ b clcomeox </ b mediated cationic ring 3 </ sub 2 </ sup monomer electronic structure 6 </ sub ε ‑ caprolactone 2 -< (< b opening homo comonomer reactivity >< sup r </ mediated polymerization theoretical foundation structural parameters reaction intermediates experimental observations enhanced zr designing well cp bonding controlled architectures cocatalyst system c – atomic charges >- oxazolines 2x level |
| status_str | publishedVersion |
| title | Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFT |
| title_full | Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFT |
| title_fullStr | Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFT |
| title_full_unstemmed | Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFT |
| title_short | Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFT |
| title_sort | Origin of Comonomer Reactivity in Zirconocene-Mediated Polymerization of 2‑Oxazoline and ε‑Caprolactone: Insights from DFT |
| topic | Biophysics Biochemistry Molecular Biology Evolutionary Biology Infectious Diseases Plant Biology Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified sequence preference stems phox initiation promotes gibbs activation energies electron density distributions defined block copolymers consecutive phox insertions bond insertion mechanisms 2 ‑ oxazoline rapid ring opening clear reactivity trend phoxcomeox </ b phoxcocl </ b meoxcophox </ b clcophox </ b clcomeox </ b mediated cationic ring 3 </ sub 2 </ sup monomer electronic structure 6 </ sub ε ‑ caprolactone 2 -< (< b opening homo comonomer reactivity >< sup r </ mediated polymerization theoretical foundation structural parameters reaction intermediates experimental observations enhanced zr designing well cp bonding controlled architectures cocatalyst system c – atomic charges >- oxazolines 2x level |