Unraveling the Effect of Chemical Environment on Half‐Sandwich Cp*ReO3 Complex Stability in Deoxydehydration Reaction.
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| Title: | Unraveling the Effect of Chemical Environment on Half‐Sandwich Cp*ReO |
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| Authors: | Wang, Han1 (AUTHOR), Murjani, Bhushan2 (AUTHOR), Gandelman, Mark3 (AUTHOR), Jentoft, Friederike C.2 (AUTHOR) fcjentoft@umass.edu, Gazit, Oz M.1 (AUTHOR) ozg@technion.ac.il |
| Source: | ChemCatChem. Jun2026, Vol. 18 Issue 11, p1-9. 9p. |
| Subjects: | Rhenium catalysts, Homogeneous catalysis, Ligands (Chemistry), Deoxygenation, Chemical kinetics |
| Abstract: | Understanding the identity of catalytically active species remains a central challenge in rhenium‐catalyzed deoxydehydration (DODH) of biomass‐derived vicinal diols. Here we revisit the scarcely studied Cp*ReO3 complex, despite being the first reported homogeneous DODH catalyst, as a mechanistic model to elucidate catalyst speciation and activity relationships. Using the conversion of 1,2‐propanediol to propylene, a transformation that has received little attention and is shown here to produce pure propylene, we quantitatively analyze reaction kinetics and catalyst speciation. Our results reveal a dynamic equilibrium between intact Cp*ReO2 complexes, Cp*‐less rhenium species, and polymerized rhenium species. The reaction environment strongly governs catalyst speciation, as nonpolar solvents promote ligand dissociation of Cp*ReO2, whereas polar solvents stabilize intact Cp*ReO2 complexes. Kinetic analysis demonstrates that in d6‐benzene, a common DODH solvent, the Cp*‐less rhenium species are 54‐fold more active than the intact Cp*ReO2 complexes, identifying them as the dominant catalytic contributors. We further show that substrate coordination stabilizes reduced rhenium centers and prevents catalyst polymerization, while simultaneously promoting ligand dissociation. Extending these insights to other vicinal diols, Cp*ReO3 also catalyzes the DODH of diethyl tartrate at room temperature. Together, these findings position Cp*ReO3 as a benchmark platform for mechanistic and stability studies in homogeneous DODH catalysis. [ABSTRACT FROM AUTHOR] |
| Copyright of ChemCatChem is the property of Wiley-Blackwell 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 |
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| Items | – Name: Title Label: Title Group: Ti Data: Unraveling the Effect of Chemical Environment on Half‐Sandwich Cp*ReO<subscript>3</subscript> Complex Stability in Deoxydehydration Reaction. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Wang%2C+Han%22">Wang, Han</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Murjani%2C+Bhushan%22">Murjani, Bhushan</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Gandelman%2C+Mark%22">Gandelman, Mark</searchLink><relatesTo>3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Jentoft%2C+Friederike+C%2E%22">Jentoft, Friederike C.</searchLink><relatesTo>2</relatesTo> (AUTHOR)<i> fcjentoft@umass.edu</i><br /><searchLink fieldCode="AR" term="%22Gazit%2C+Oz+M%2E%22">Gazit, Oz M.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> ozg@technion.ac.il</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22ChemCatChem%22">ChemCatChem</searchLink>. Jun2026, Vol. 18 Issue 11, p1-9. 9p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Rhenium+catalysts%22">Rhenium catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Homogeneous+catalysis%22">Homogeneous catalysis</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Deoxygenation%22">Deoxygenation</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+kinetics%22">Chemical kinetics</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Understanding the identity of catalytically active species remains a central challenge in rhenium‐catalyzed deoxydehydration (DODH) of biomass‐derived vicinal diols. Here we revisit the scarcely studied Cp*ReO3 complex, despite being the first reported homogeneous DODH catalyst, as a mechanistic model to elucidate catalyst speciation and activity relationships. Using the conversion of 1,2‐propanediol to propylene, a transformation that has received little attention and is shown here to produce pure propylene, we quantitatively analyze reaction kinetics and catalyst speciation. Our results reveal a dynamic equilibrium between intact Cp*ReO2 complexes, Cp*‐less rhenium species, and polymerized rhenium species. The reaction environment strongly governs catalyst speciation, as nonpolar solvents promote ligand dissociation of Cp*ReO2, whereas polar solvents stabilize intact Cp*ReO2 complexes. Kinetic analysis demonstrates that in d6‐benzene, a common DODH solvent, the Cp*‐less rhenium species are 54‐fold more active than the intact Cp*ReO2 complexes, identifying them as the dominant catalytic contributors. We further show that substrate coordination stabilizes reduced rhenium centers and prevents catalyst polymerization, while simultaneously promoting ligand dissociation. Extending these insights to other vicinal diols, Cp*ReO3 also catalyzes the DODH of diethyl tartrate at room temperature. Together, these findings position Cp*ReO3 as a benchmark platform for mechanistic and stability studies in homogeneous DODH catalysis. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of ChemCatChem is the property of Wiley-Blackwell 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: 10.1002/cctc.70809 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 9 StartPage: 1 Subjects: – SubjectFull: Rhenium catalysts Type: general – SubjectFull: Homogeneous catalysis Type: general – SubjectFull: Ligands (Chemistry) Type: general – SubjectFull: Deoxygenation Type: general – SubjectFull: Chemical kinetics Type: general Titles: – TitleFull: Unraveling the Effect of Chemical Environment on Half‐Sandwich Cp*ReO3 Complex Stability in Deoxydehydration Reaction. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Wang, Han – PersonEntity: Name: NameFull: Murjani, Bhushan – PersonEntity: Name: NameFull: Gandelman, Mark – PersonEntity: Name: NameFull: Jentoft, Friederike C. – PersonEntity: Name: NameFull: Gazit, Oz M. IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 06 Text: Jun2026 Type: published Y: 2026 Identifiers: – Type: issn-print Value: 18673880 Numbering: – Type: volume Value: 18 – Type: issue Value: 11 Titles: – TitleFull: ChemCatChem Type: main |
| ResultId | 1 |
