A tridentate and dianionic N-heterocyclic olefin (NHO) with two unsymmetrically-tethered aryloxide sidearms on bismuth: a fortuitous followed by systematic discovery.
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| Title: | A tridentate and dianionic N-heterocyclic olefin (NHO) with two unsymmetrically-tethered aryloxide sidearms on bismuth: a fortuitous followed by systematic discovery. |
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| Authors: | Goswami, Santu1 (AUTHOR), Sarkar, Subham1,2 (AUTHOR), Guha Roy, Anisha1 (AUTHOR), Mallick, Dibyendu2 (AUTHOR) dibyendu.chem@presiuniv.ac.in, Mukherjee, Debabrata1 (AUTHOR) d.mukherjee@iiserkol.ac.in |
| Source: | Dalton Transactions: An International Journal of Inorganic Chemistry. 5/28/2025, Vol. 54 Issue 20, p8142-8151. 10p. |
| Subjects: | Bismuth compounds, Ligands (Chemistry), Heterocyclic compounds, Chemical reactions, Ab-initio calculations, Imidazoles, Aryl group |
| Abstract: | Herein, we report our previously developed bifunctional imidaozlium-phenol LH2Br ([HO-4,6-tBu2-C6H2-2-CH2{CH(NCH = CHNAr)}]Br; Ar = Dipp = 2,6-iPr2-C6H3), leading to three distinct outcomes with bismuth by simply altering the relative ratios of the reacting components. Treating LH2Br and Bi(HMDS)3 (HMDS = N(SiMe3)2) in a 1 : 1 ratio gives the NHC-Bi complex [(L)BiBr(HMDS)] (1). In contrast, LH2Br , Bi(HMDS)3, and KHMDS in a 2 : 1 : 1 ratio serendipitously result in an unprecedented NHO-Bi complex [(DippNHO2ArO)BiBr] (2), featuring a novel dianoinic and tridentate NHO ligand with two unsymmetric aryloxide sidearms. A tri-acidic imidazolium salt L′H3I ([HO-4,6-tBu2-C6H2-2-CH2{C(HO-4,6-tBu2-C6H2-2-CH2)(NCH = CHNMe)}]I) is synthesized independently as a potential precursor to such an NHO framework, and the corresponding NHO-BiI complex [(MeNHO2ArO)Bi(μ-I)]2 (32) is made as proof of concept. Lastly, treating LH2Br and Bi(HMDS)3 in a 2 : 1 ratio also unexpectedly leads to an 'abnormal' NHC-Bi complex [(aL)BiBr2(DippImd)] (4; DippImd = Dipp-imidazole). The multi-component and essentially multi-step reactions leading to 2 and 4 are challenging to fully elucidate mechanistically. Still, control experiments indicate 1 as a possible intermediate in both cases. Based on these results and prior insights into LH2Br and an intermediate LH , plausible routes for both 2 and 4 are hypothesized. DFT calculations are also performed to analyze the bonding in 2 and 32 and to justify an NHC to aNHC isomerization towards the formation of 4. [ABSTRACT FROM AUTHOR] |
| Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 185283407 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: A tridentate and dianionic N-heterocyclic olefin (NHO) with two unsymmetrically-tethered aryloxide sidearms on bismuth: a fortuitous followed by systematic discovery. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Goswami%2C+Santu%22">Goswami, Santu</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Sarkar%2C+Subham%22">Sarkar, Subham</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Guha+Roy%2C+Anisha%22">Guha Roy, Anisha</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Mallick%2C+Dibyendu%22">Mallick, Dibyendu</searchLink><relatesTo>2</relatesTo> (AUTHOR)<i> dibyendu.chem@presiuniv.ac.in</i><br /><searchLink fieldCode="AR" term="%22Mukherjee%2C+Debabrata%22">Mukherjee, Debabrata</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> d.mukherjee@iiserkol.ac.in</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 5/28/2025, Vol. 54 Issue 20, p8142-8151. 10p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Bismuth+compounds%22">Bismuth compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Heterocyclic+compounds%22">Heterocyclic compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Ab-initio+calculations%22">Ab-initio calculations</searchLink><br /><searchLink fieldCode="DE" term="%22Imidazoles%22">Imidazoles</searchLink><br /><searchLink fieldCode="DE" term="%22Aryl+group%22">Aryl group</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Herein, we report our previously developed bifunctional imidaozlium-phenol LH2Br ([HO-4,6-tBu2-C6H2-2-CH2{CH(NCH = CHNAr)}]Br; Ar = Dipp = 2,6-iPr2-C6H3), leading to three distinct outcomes with bismuth by simply altering the relative ratios of the reacting components. Treating LH2Br and Bi(HMDS)3 (HMDS = N(SiMe3)2) in a 1 : 1 ratio gives the NHC-Bi complex [(L)BiBr(HMDS)] (1). In contrast, LH2Br , Bi(HMDS)3, and KHMDS in a 2 : 1 : 1 ratio serendipitously result in an unprecedented NHO-Bi complex [(DippNHO2ArO)BiBr] (2), featuring a novel dianoinic and tridentate NHO ligand with two unsymmetric aryloxide sidearms. A tri-acidic imidazolium salt L′H3I ([HO-4,6-tBu2-C6H2-2-CH2{C(HO-4,6-tBu2-C6H2-2-CH2)(NCH = CHNMe)}]I) is synthesized independently as a potential precursor to such an NHO framework, and the corresponding NHO-BiI complex [(MeNHO2ArO)Bi(μ-I)]2 (32) is made as proof of concept. Lastly, treating LH2Br and Bi(HMDS)3 in a 2 : 1 ratio also unexpectedly leads to an 'abnormal' NHC-Bi complex [(aL)BiBr2(DippImd)] (4; DippImd = Dipp-imidazole). The multi-component and essentially multi-step reactions leading to 2 and 4 are challenging to fully elucidate mechanistically. Still, control experiments indicate 1 as a possible intermediate in both cases. Based on these results and prior insights into LH2Br and an intermediate LH , plausible routes for both 2 and 4 are hypothesized. DFT calculations are also performed to analyze the bonding in 2 and 32 and to justify an NHC to aNHC isomerization towards the formation of 4. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1039/d5dt00706b Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 10 StartPage: 8142 Subjects: – SubjectFull: Bismuth compounds Type: general – SubjectFull: Ligands (Chemistry) Type: general – SubjectFull: Heterocyclic compounds Type: general – SubjectFull: Chemical reactions Type: general – SubjectFull: Ab-initio calculations Type: general – SubjectFull: Imidazoles Type: general – SubjectFull: Aryl group Type: general Titles: – TitleFull: A tridentate and dianionic N-heterocyclic olefin (NHO) with two unsymmetrically-tethered aryloxide sidearms on bismuth: a fortuitous followed by systematic discovery. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Goswami, Santu – PersonEntity: Name: NameFull: Sarkar, Subham – PersonEntity: Name: NameFull: Guha Roy, Anisha – PersonEntity: Name: NameFull: Mallick, Dibyendu – PersonEntity: Name: NameFull: Mukherjee, Debabrata IsPartOfRelationships: – BibEntity: Dates: – D: 28 M: 05 Text: 5/28/2025 Type: published Y: 2025 Identifiers: – Type: issn-print Value: 14779226 Numbering: – Type: volume Value: 54 – Type: issue Value: 20 Titles: – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry Type: main |
| ResultId | 1 |
