Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex
A nickel-silylene complex is shown to reversibly activate benzene via C–H bond activation at ambient temperature. The benzene C–H bond formally adds across the Ni–Si core to form a nickel-silyl complex with an H–Si–Ni–Ph linkage bearing a highly covalent Ni–Si bond (2.2363(6) Å). Dissolution of this...
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2025
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| _version_ | 1852018092141445120 |
|---|---|
| author | Leon Gomm (21811882) |
| author2 | Hui Zhu (87035) Gregor Schnakenburg (1393753) Senada Nozinovic (2280559) Stefan Grimme (1321575) Connie C. Lu (1455736) |
| author2_role | author author author author author |
| author_facet | Leon Gomm (21811882) Hui Zhu (87035) Gregor Schnakenburg (1393753) Senada Nozinovic (2280559) Stefan Grimme (1321575) Connie C. Lu (1455736) |
| author_role | author |
| dc.creator.none.fl_str_mv | Leon Gomm (21811882) Hui Zhu (87035) Gregor Schnakenburg (1393753) Senada Nozinovic (2280559) Stefan Grimme (1321575) Connie C. Lu (1455736) |
| dc.date.none.fl_str_mv | 2025-07-30T08:03:26Z |
| dc.identifier.none.fl_str_mv | 10.1021/jacs.5c10922.s002 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/dataset/Reversible_C_H_Bond_Activation_of_Unactivated_Arenes_by_a_Nickel-Silylene_Complex/29673145 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biophysics Biochemistry Cell Biology Cancer Science Policy Hematology Environmental Sciences not elsewhere classified Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified g ., toluene concerted oxidative addition arene initially forms neat arene solvent å ). unactivated arenes silylene complex silyl complex resultant hydride redox burden facile reversibility complete conversion ambient temperature 0 ), |
| dc.title.none.fl_str_mv | Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex |
| dc.type.none.fl_str_mv | Dataset info:eu-repo/semantics/publishedVersion dataset |
| description | A nickel-silylene complex is shown to reversibly activate benzene via C–H bond activation at ambient temperature. The benzene C–H bond formally adds across the Ni–Si core to form a nickel-silyl complex with an H–Si–Ni–Ph linkage bearing a highly covalent Ni–Si bond (2.2363(6) Å). Dissolution of this product in neat arene solvent, e.g., toluene, trifluorotoluene, or anisole, resulted in the complete conversion to the aryl C–H activated product of the solvent and, thereby, demonstrates the facile reversibility of C–H bond activation across the Ni–Si core. The various arene C–H bond activations by the reactive Ni(0)-silylene species were investigated using density functional theory calculations. In all cases, the arene initially forms an η<sup>2</sup>-adduct to Ni(0), and then C–H activation proceeds via a concerted oxidative addition at only the Ni center. The Si center assists C–H bond activation by sharing the redox burden with Ni while stabilizing the resultant hydride. |
| eu_rights_str_mv | openAccess |
| id | Manara_3e7a1045c05cbbfcda336b7cfe7ec7d5 |
| identifier_str_mv | 10.1021/jacs.5c10922.s002 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/29673145 |
| 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 | Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene ComplexLeon Gomm (21811882)Hui Zhu (87035)Gregor Schnakenburg (1393753)Senada Nozinovic (2280559)Stefan Grimme (1321575)Connie C. Lu (1455736)BiophysicsBiochemistryCell BiologyCancerScience PolicyHematologyEnvironmental Sciences not elsewhere classifiedBiological Sciences not elsewhere classifiedChemical Sciences not elsewhere classifiedg ., tolueneconcerted oxidative additionarene initially formsneat arene solventå ).unactivated arenessilylene complexsilyl complexresultant hydrideredox burdenfacile reversibilitycomplete conversionambient temperature0 ),A nickel-silylene complex is shown to reversibly activate benzene via C–H bond activation at ambient temperature. The benzene C–H bond formally adds across the Ni–Si core to form a nickel-silyl complex with an H–Si–Ni–Ph linkage bearing a highly covalent Ni–Si bond (2.2363(6) Å). Dissolution of this product in neat arene solvent, e.g., toluene, trifluorotoluene, or anisole, resulted in the complete conversion to the aryl C–H activated product of the solvent and, thereby, demonstrates the facile reversibility of C–H bond activation across the Ni–Si core. The various arene C–H bond activations by the reactive Ni(0)-silylene species were investigated using density functional theory calculations. In all cases, the arene initially forms an η<sup>2</sup>-adduct to Ni(0), and then C–H activation proceeds via a concerted oxidative addition at only the Ni center. The Si center assists C–H bond activation by sharing the redox burden with Ni while stabilizing the resultant hydride.2025-07-30T08:03:26ZDatasetinfo:eu-repo/semantics/publishedVersiondataset10.1021/jacs.5c10922.s002https://figshare.com/articles/dataset/Reversible_C_H_Bond_Activation_of_Unactivated_Arenes_by_a_Nickel-Silylene_Complex/29673145CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/296731452025-07-30T08:03:26Z |
| spellingShingle | Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex Leon Gomm (21811882) Biophysics Biochemistry Cell Biology Cancer Science Policy Hematology Environmental Sciences not elsewhere classified Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified g ., toluene concerted oxidative addition arene initially forms neat arene solvent å ). unactivated arenes silylene complex silyl complex resultant hydride redox burden facile reversibility complete conversion ambient temperature 0 ), |
| status_str | publishedVersion |
| title | Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex |
| title_full | Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex |
| title_fullStr | Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex |
| title_full_unstemmed | Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex |
| title_short | Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex |
| title_sort | Reversible C–H Bond Activation of Unactivated Arenes by a Nickel-Silylene Complex |
| topic | Biophysics Biochemistry Cell Biology Cancer Science Policy Hematology Environmental Sciences not elsewhere classified Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified g ., toluene concerted oxidative addition arene initially forms neat arene solvent å ). unactivated arenes silylene complex silyl complex resultant hydride redox burden facile reversibility complete conversion ambient temperature 0 ), |