Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride Transfer
The mechanisms and dynamics of bimolecular nucleophilic substitution (S<sub>N</sub>2) reactions are complex and influenced by the nature of the central atom. In this study, we explore S<sub>N</sub>2 at a nitrogen center (S<sub>N</sub>2@N) by investigating the reac...
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2024
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| _version_ | 1852025083358347264 |
|---|---|
| author | Siddharth Sankar Dutta (20293126) |
| author2 | Upakarasamy Lourderaj (2480632) |
| author2_role | author |
| author_facet | Siddharth Sankar Dutta (20293126) Upakarasamy Lourderaj (2480632) |
| author_role | author |
| dc.creator.none.fl_str_mv | Siddharth Sankar Dutta (20293126) Upakarasamy Lourderaj (2480632) |
| dc.date.none.fl_str_mv | 2024-11-20T01:29:36Z |
| dc.identifier.none.fl_str_mv | 10.1021/acs.jpca.4c06805.s002 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/media/Unconventional_Pathways_in_Nitrogen-Centered_S_sub_N_sub_2_Reactions_From_Roundabout_to_Hydride_Transfer/27859564 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biochemistry Microbiology Infectious Diseases Plant Biology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified traditional direct rebound sup >–</ sup fc )/ aug bimolecular nucleophilic substitution transfer pathway leading 3 </ sub 2 </ sub roundabout pathways alongside n </ sub 2 product formation unconventional pathways hydride transfer umbrella inversion quantitative agreement pvdz level novel hydride methoxide ion group resulting experimental data energy proton central atom |
| dc.title.none.fl_str_mv | Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride Transfer |
| dc.type.none.fl_str_mv | Dataset Media info:eu-repo/semantics/publishedVersion dataset |
| description | The mechanisms and dynamics of bimolecular nucleophilic substitution (S<sub>N</sub>2) reactions are complex and influenced by the nature of the central atom. In this study, we explore S<sub>N</sub>2 at a nitrogen center (S<sub>N</sub>2@N) by investigating the reaction of chloramine (NH<sub>2</sub>Cl) with methoxide ion (CH<sub>3</sub>O<sup>–</sup>) using ab initio classical trajectory simulations at the MP2(fc)/aug-cc-pVDZ level of theory. We observe that, in addition to the expected S<sub>N</sub>2 product formation (CH<sub>3</sub>ONH<sub>2</sub> + Cl<sup>–</sup>), a high-energy proton-transfer pathway leading to CH<sub>3</sub>OH and NHCl<sup>–</sup> dominates, with near-quantitative agreement between simulations and experimental data. Notably, we identify a novel hydride-transfer pathway yielding NH<sub>3</sub>, H<sub>2</sub>CO, and Cl<sup>–</sup>, revealing alternative reactivity channels previously uncharacterized in nitrogen-centered S<sub>N</sub>2 reactions. Mechanistic analysis uncovers unconventional roaming-mediated and roundabout pathways alongside the traditional direct rebound and indirect mechanisms. Additionally, an umbrella inversion of the NH<sub>2</sub> group resulting in retention of configuration in the CH<sub>3</sub>ONH<sub>2</sub> product was observed in a fraction of trajectories. |
| eu_rights_str_mv | openAccess |
| id | Manara_2781363d2c4affcaf7a66cdcb4e9b91c |
| identifier_str_mv | 10.1021/acs.jpca.4c06805.s002 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/27859564 |
| publishDate | 2024 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY-NC 4.0 |
| spelling | Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride TransferSiddharth Sankar Dutta (20293126)Upakarasamy Lourderaj (2480632)BiochemistryMicrobiologyInfectious DiseasesPlant BiologyBiological Sciences not elsewhere classifiedChemical Sciences not elsewhere classifiedtraditional direct reboundsup >–</ supfc )/ augbimolecular nucleophilic substitutiontransfer pathway leading3 </ sub2 </ subroundabout pathways alongsiden </ sub2 product formationunconventional pathwayshydride transferumbrella inversionquantitative agreementpvdz levelnovel hydridemethoxide iongroup resultingexperimental dataenergy protoncentral atomThe mechanisms and dynamics of bimolecular nucleophilic substitution (S<sub>N</sub>2) reactions are complex and influenced by the nature of the central atom. In this study, we explore S<sub>N</sub>2 at a nitrogen center (S<sub>N</sub>2@N) by investigating the reaction of chloramine (NH<sub>2</sub>Cl) with methoxide ion (CH<sub>3</sub>O<sup>–</sup>) using ab initio classical trajectory simulations at the MP2(fc)/aug-cc-pVDZ level of theory. We observe that, in addition to the expected S<sub>N</sub>2 product formation (CH<sub>3</sub>ONH<sub>2</sub> + Cl<sup>–</sup>), a high-energy proton-transfer pathway leading to CH<sub>3</sub>OH and NHCl<sup>–</sup> dominates, with near-quantitative agreement between simulations and experimental data. Notably, we identify a novel hydride-transfer pathway yielding NH<sub>3</sub>, H<sub>2</sub>CO, and Cl<sup>–</sup>, revealing alternative reactivity channels previously uncharacterized in nitrogen-centered S<sub>N</sub>2 reactions. Mechanistic analysis uncovers unconventional roaming-mediated and roundabout pathways alongside the traditional direct rebound and indirect mechanisms. Additionally, an umbrella inversion of the NH<sub>2</sub> group resulting in retention of configuration in the CH<sub>3</sub>ONH<sub>2</sub> product was observed in a fraction of trajectories.2024-11-20T01:29:36ZDatasetMediainfo:eu-repo/semantics/publishedVersiondataset10.1021/acs.jpca.4c06805.s002https://figshare.com/articles/media/Unconventional_Pathways_in_Nitrogen-Centered_S_sub_N_sub_2_Reactions_From_Roundabout_to_Hydride_Transfer/27859564CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/278595642024-11-20T01:29:36Z |
| spellingShingle | Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride Transfer Siddharth Sankar Dutta (20293126) Biochemistry Microbiology Infectious Diseases Plant Biology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified traditional direct rebound sup >–</ sup fc )/ aug bimolecular nucleophilic substitution transfer pathway leading 3 </ sub 2 </ sub roundabout pathways alongside n </ sub 2 product formation unconventional pathways hydride transfer umbrella inversion quantitative agreement pvdz level novel hydride methoxide ion group resulting experimental data energy proton central atom |
| status_str | publishedVersion |
| title | Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride Transfer |
| title_full | Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride Transfer |
| title_fullStr | Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride Transfer |
| title_full_unstemmed | Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride Transfer |
| title_short | Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride Transfer |
| title_sort | Unconventional Pathways in Nitrogen-Centered S<sub>N</sub>2 Reactions: From Roundabout to Hydride Transfer |
| topic | Biochemistry Microbiology Infectious Diseases Plant Biology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified traditional direct rebound sup >–</ sup fc )/ aug bimolecular nucleophilic substitution transfer pathway leading 3 </ sub 2 </ sub roundabout pathways alongside n </ sub 2 product formation unconventional pathways hydride transfer umbrella inversion quantitative agreement pvdz level novel hydride methoxide ion group resulting experimental data energy proton central atom |