Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> Complex
The direct splitting of H<sub>2</sub> and N<sub>2</sub> molecules is a challenging reaction that is closely related to the Haber–Bosch ammonia synthesis process. Until now, such reactivity has never been observed in the case of molecular lanthanide species. Here, we show that...
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| مؤلفون آخرون: | , , , , , |
| منشور في: |
2025
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| _version_ | 1852022300690350080 |
|---|---|
| author | Evangelos Papangelis (20831910) |
| author2 | Luca Demonti (20831913) Iker del Rosal (8556855) Angus Shephard (20831916) Laurent Maron (1346082) Grégory Nocton (1478341) Thomas Simler (1498453) |
| author2_role | author author author author author author |
| author_facet | Evangelos Papangelis (20831910) Luca Demonti (20831913) Iker del Rosal (8556855) Angus Shephard (20831916) Laurent Maron (1346082) Grégory Nocton (1478341) Thomas Simler (1498453) |
| author_role | author |
| dc.creator.none.fl_str_mv | Evangelos Papangelis (20831910) Luca Demonti (20831913) Iker del Rosal (8556855) Angus Shephard (20831916) Laurent Maron (1346082) Grégory Nocton (1478341) Thomas Simler (1498453) |
| dc.date.none.fl_str_mv | 2025-03-05T13:11:55Z |
| dc.identifier.none.fl_str_mv | 10.1021/jacs.4c18416.s002 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/dataset/Room-Temperature_H_sub_2_sub_Splitting_and_N_sub_2_sub_Hydrogenation_Induced_by_a_Neutral_Lu_sup_II_sup_Complex/28540590 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biophysics Biochemistry Microbiology Genetics Molecular Biology Sociology Cancer Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified valent molecular rare ligand scaffold allows earth metal complexes molecular lanthanide species ii </ sup 2 –</ sup highly reactive lu 2 bar h 2 </ sub lanthanide chemistry unique lu temperature h smooth conditions neutral lu kinetically stable fully corroborated dft calculations coordinated diazenido closely related challenging reaction careful selection |
| dc.title.none.fl_str_mv | Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> Complex |
| dc.type.none.fl_str_mv | Dataset info:eu-repo/semantics/publishedVersion dataset |
| description | The direct splitting of H<sub>2</sub> and N<sub>2</sub> molecules is a challenging reaction that is closely related to the Haber–Bosch ammonia synthesis process. Until now, such reactivity has never been observed in the case of molecular lanthanide species. Here, we show that careful selection of the ligand scaffold allows the isolation and characterization of a kinetically stable but highly reactive Lu<sup>II</sup> complex. This divalent lanthanide species enables direct H<sub>2</sub> splitting at room temperature, an unknown reactivity in lanthanide chemistry, which has been fully corroborated by DFT calculations. In addition, the Lu<sup>II</sup> complex readily binds N<sub>2</sub>, leading to an end-on coordinated diazenido (N<sub>2</sub>)<sup>2–</sup> lanthanide complex. The latter can be hydrogenated under very smooth conditions (ca. 1.2 bar H<sub>2</sub>, ambient temperature) to form a unique Lu<sup>III</sup>–NH<sub>2</sub> complex. Direct N<sub>2</sub> hydrogenation and cleavage are thus accessible using low-valent molecular rare-earth metal complexes. |
| eu_rights_str_mv | openAccess |
| id | Manara_43024112deee2fc45fba0da5f072f19e |
| identifier_str_mv | 10.1021/jacs.4c18416.s002 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/28540590 |
| 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 | Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> ComplexEvangelos Papangelis (20831910)Luca Demonti (20831913)Iker del Rosal (8556855)Angus Shephard (20831916)Laurent Maron (1346082)Grégory Nocton (1478341)Thomas Simler (1498453)BiophysicsBiochemistryMicrobiologyGeneticsMolecular BiologySociologyCancerBiological Sciences not elsewhere classifiedChemical Sciences not elsewhere classifiedvalent molecular rareligand scaffold allowsearth metal complexesmolecular lanthanide speciesii </ sup2 –</ suphighly reactive lu2 bar h2 </ sublanthanide chemistryunique lutemperature hsmooth conditionsneutral lukinetically stablefully corroborateddft calculationscoordinated diazenidoclosely relatedchallenging reactioncareful selectionThe direct splitting of H<sub>2</sub> and N<sub>2</sub> molecules is a challenging reaction that is closely related to the Haber–Bosch ammonia synthesis process. Until now, such reactivity has never been observed in the case of molecular lanthanide species. Here, we show that careful selection of the ligand scaffold allows the isolation and characterization of a kinetically stable but highly reactive Lu<sup>II</sup> complex. This divalent lanthanide species enables direct H<sub>2</sub> splitting at room temperature, an unknown reactivity in lanthanide chemistry, which has been fully corroborated by DFT calculations. In addition, the Lu<sup>II</sup> complex readily binds N<sub>2</sub>, leading to an end-on coordinated diazenido (N<sub>2</sub>)<sup>2–</sup> lanthanide complex. The latter can be hydrogenated under very smooth conditions (ca. 1.2 bar H<sub>2</sub>, ambient temperature) to form a unique Lu<sup>III</sup>–NH<sub>2</sub> complex. Direct N<sub>2</sub> hydrogenation and cleavage are thus accessible using low-valent molecular rare-earth metal complexes.2025-03-05T13:11:55ZDatasetinfo:eu-repo/semantics/publishedVersiondataset10.1021/jacs.4c18416.s002https://figshare.com/articles/dataset/Room-Temperature_H_sub_2_sub_Splitting_and_N_sub_2_sub_Hydrogenation_Induced_by_a_Neutral_Lu_sup_II_sup_Complex/28540590CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/285405902025-03-05T13:11:55Z |
| spellingShingle | Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> Complex Evangelos Papangelis (20831910) Biophysics Biochemistry Microbiology Genetics Molecular Biology Sociology Cancer Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified valent molecular rare ligand scaffold allows earth metal complexes molecular lanthanide species ii </ sup 2 –</ sup highly reactive lu 2 bar h 2 </ sub lanthanide chemistry unique lu temperature h smooth conditions neutral lu kinetically stable fully corroborated dft calculations coordinated diazenido closely related challenging reaction careful selection |
| status_str | publishedVersion |
| title | Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> Complex |
| title_full | Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> Complex |
| title_fullStr | Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> Complex |
| title_full_unstemmed | Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> Complex |
| title_short | Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> Complex |
| title_sort | Room-Temperature H<sub>2</sub> Splitting and N<sub>2</sub>‑Hydrogenation Induced by a Neutral Lu<sup>II</sup> Complex |
| topic | Biophysics Biochemistry Microbiology Genetics Molecular Biology Sociology Cancer Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified valent molecular rare ligand scaffold allows earth metal complexes molecular lanthanide species ii </ sup 2 –</ sup highly reactive lu 2 bar h 2 </ sub lanthanide chemistry unique lu temperature h smooth conditions neutral lu kinetically stable fully corroborated dft calculations coordinated diazenido closely related challenging reaction careful selection |