Synthesis, structure & diphenylacetylene reduction reactivity of a carbide-supported Fe4Mo2 carbonyl cluster: a higher Fe-valence hydride intermediate for enhanced selectivity.
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| Title: | Synthesis, structure & diphenylacetylene reduction reactivity of a carbide-supported Fe |
|---|---|
| Authors: | Dick, Emily1 (AUTHOR), Joseph, Chris1 (AUTHOR), Lynch, Vincent M.1 (AUTHOR), Rose, Michael J.1 (AUTHOR) mrose@cm.utexas.edu |
| Source: | Dalton Transactions: An International Journal of Inorganic Chemistry. 6/9/2026, Vol. 55 Issue 22, p8655-8662. 8p. |
| Subjects: | Catalyst selectivity, Metal clusters, Diphenylacetylene, Catalysis, X-ray crystallography, Hydrides |
| Abstract: | The novel four-iron, two-molybdenum cluster [(µ6-C)Fe4Mo2(CO)18]2− (2) containing an interstitial carbide has been structurally characterized and prepared from the corresponding Fe4 dianion [(µ4-C)Fe4(CO)12]2− (1) supported by two crowned alkali units in [K(benzo-18-crown-6)]+. In the X-ray structure of 2 , the two molybdenum atoms share an internal geometry of a cis orientation about the central carbide, which indicates the stability of the well-known 'butterfly' Fe4C core found in the precursor 1 , and this finding is consistent with other bis-heterometal variants of general formula [Fe4M2] (M = Ni, Cu, Rh, Au). Reactivity studies monitoring the reduction of diphenylacetylene (DPA) catalyzed by 2 showed selective reduction to cis-diphenylethylene. The effect of proton source pKa and steric bulk on DPA reduction demonstrated that product selectivity is enhanced with increased steric bulk near the protonation site, and that conversion increases with more acidic proton sources. Overall, increased selectivity is observed with 2 compared with catalyst-free reactions, Fe-only clusters and the Fe5Mo variant. We attribute the beneficial reactivity profile of cluster 2 to the electronic effect of the two Mo(0) centers, which lead to higher valent iron sites in the hydride intermediate cluster(s), thus decreasing non-specific reduction and increasing selectivity. [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: 194430951 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Synthesis, structure & diphenylacetylene reduction reactivity of a carbide-supported Fe<subscript>4</subscript>Mo<subscript>2</subscript> carbonyl cluster: a higher Fe-valence hydride intermediate for enhanced selectivity. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Dick%2C+Emily%22">Dick, Emily</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Joseph%2C+Chris%22">Joseph, Chris</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Lynch%2C+Vincent+M%2E%22">Lynch, Vincent M.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Rose%2C+Michael+J%2E%22">Rose, Michael J.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> mrose@cm.utexas.edu</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>. 6/9/2026, Vol. 55 Issue 22, p8655-8662. 8p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Catalyst+selectivity%22">Catalyst selectivity</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+clusters%22">Metal clusters</searchLink><br /><searchLink fieldCode="DE" term="%22Diphenylacetylene%22">Diphenylacetylene</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysis%22">Catalysis</searchLink><br /><searchLink fieldCode="DE" term="%22X-ray+crystallography%22">X-ray crystallography</searchLink><br /><searchLink fieldCode="DE" term="%22Hydrides%22">Hydrides</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The novel four-iron, two-molybdenum cluster [(µ6-C)Fe4Mo2(CO)18]2− (2) containing an interstitial carbide has been structurally characterized and prepared from the corresponding Fe4 dianion [(µ4-C)Fe4(CO)12]2− (1) supported by two crowned alkali units in [K(benzo-18-crown-6)]+. In the X-ray structure of 2 , the two molybdenum atoms share an internal geometry of a cis orientation about the central carbide, which indicates the stability of the well-known 'butterfly' Fe4C core found in the precursor 1 , and this finding is consistent with other bis-heterometal variants of general formula [Fe4M2] (M = Ni, Cu, Rh, Au). Reactivity studies monitoring the reduction of diphenylacetylene (DPA) catalyzed by 2 showed selective reduction to cis-diphenylethylene. The effect of proton source pKa and steric bulk on DPA reduction demonstrated that product selectivity is enhanced with increased steric bulk near the protonation site, and that conversion increases with more acidic proton sources. Overall, increased selectivity is observed with 2 compared with catalyst-free reactions, Fe-only clusters and the Fe5Mo variant. We attribute the beneficial reactivity profile of cluster 2 to the electronic effect of the two Mo(0) centers, which lead to higher valent iron sites in the hydride intermediate cluster(s), thus decreasing non-specific reduction and increasing selectivity. [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/d6dt00524a Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 8 StartPage: 8655 Subjects: – SubjectFull: Catalyst selectivity Type: general – SubjectFull: Metal clusters Type: general – SubjectFull: Diphenylacetylene Type: general – SubjectFull: Catalysis Type: general – SubjectFull: X-ray crystallography Type: general – SubjectFull: Hydrides Type: general Titles: – TitleFull: Synthesis, structure & diphenylacetylene reduction reactivity of a carbide-supported Fe4Mo2 carbonyl cluster: a higher Fe-valence hydride intermediate for enhanced selectivity. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Dick, Emily – PersonEntity: Name: NameFull: Joseph, Chris – PersonEntity: Name: NameFull: Lynch, Vincent M. – PersonEntity: Name: NameFull: Rose, Michael J. IsPartOfRelationships: – BibEntity: Dates: – D: 09 M: 06 Text: 6/9/2026 Type: published Y: 2026 Identifiers: – Type: issn-print Value: 14779226 Numbering: – Type: volume Value: 55 – Type: issue Value: 22 Titles: – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry Type: main |
| ResultId | 1 |
