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Terminal Mo Carbide and Carbyne Reactivity: H₂ Cleavage, B–C Bond Activation, and C–C Coupling

Bailey, Gwendolyn A. and Agapie, Theodor (2021) Terminal Mo Carbide and Carbyne Reactivity: H₂ Cleavage, B–C Bond Activation, and C–C Coupling. Organometallics, 40 (16). pp. 2881-2887. ISSN 0276-7333. doi:10.1021/acs.organomet.1c00336. https://resolver.caltech.edu/CaltechAUTHORS:20210830-230028871

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Abstract

Transition-metal carbides have been posited as intermediates in the upgrading of C₁ feedstocks, including the Fischer–Tropsch synthesis of higher olefins from CO and H₂. Still, molecular examples remain rare, and their reactivity is poorly understood. In a molecular platform supported by a flexible terphenyl diphosphine ligand, the important C–C coupling step was previously demonstrated on the reaction of Mo carbide and carbene species with CO. Methylidyne and methylidene complexes were accessible on sequential treatment of the carbide with sources of H⁺ and H⁻, surrogates for heterolyzed H₂. Herein, we demonstrate that the terminal carbide complex is also capable of directly activating H₂, yielding a P–C-bonded ylide complex. The carbide moiety also inserts into the B–C bond of triphenylborane, yielding an unusual example of a borylcarbene with a direct Mo–B contact. C–C coupling from the terminal methylidyne, a potential intermediate formed on heterolytic H₂ cleavage and H⁺ transfer to the carbide, yields a Mo ketenyl complex, thus giving information for the first time on the relative rates of coupling from carbide, carbyne, and carbene species in the same molecular platform.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.organomet.1c00336DOIArticle
ORCID:
AuthorORCID
Bailey, Gwendolyn A.0000-0002-6636-4128
Agapie, Theodor0000-0002-9692-7614
Alternate Title:Terminal Mo Carbide and Carbyne Reactivity: H2 Cleavage, B–C Bond Activation, and C–C Coupling
Additional Information:© 2021 American Chemical Society. Received 6 June 2021. Published online 12 August 2021. Published in issue 23 August 2021. We thank Lawrence Henling and Michael Takase for invaluable crystallographic assistance. G.A.B. is grateful to the NSERC of Canada and the Resnick Sustainability Institute at Caltech for fellowship support. We thank the the NSF (CHE-1800501), the Dow Next Generation Education Fund (instrumentation), and Caltech for funding. The authors declare no competing financial interest. CCDC 2000078–2000079 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
NSFCHE-1800501
Dow Next Generation Educator FundUNSPECIFIED
CaltechUNSPECIFIED
Subject Keywords:Carbene compounds, Ligands, Chemical reactions, Inorganic carbon compounds, Reactivity
Issue or Number:16
DOI:10.1021/acs.organomet.1c00336
Record Number:CaltechAUTHORS:20210830-230028871
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210830-230028871
Official Citation:Terminal Mo Carbide and Carbyne Reactivity: H2 Cleavage, B–C Bond Activation, and C–C Coupling Gwendolyn A. Bailey and Theodor Agapie Organometallics 2021 40 (16), 2881-2887 DOI: 10.1021/acs.organomet.1c00336
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110627
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:31 Aug 2021 16:33
Last Modified:31 Aug 2021 16:33

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