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Molybdenum-Mediated Coupling of Carbon Monoxide to a C₃ Product on a Single Metal Site

Low, Choon Heng and Buss, Joshua A. and Agapie, Theodor (2022) Molybdenum-Mediated Coupling of Carbon Monoxide to a C₃ Product on a Single Metal Site. Inorganic Chemistry, 61 (20). pp. 7710-7714. ISSN 0020-1669. doi:10.1021/acs.inorgchem.2c00266.

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The synthesis and characterization of a series of naphthalenediyl-diphosphine molybdenum complexes are reported. A novel dicarbonyl–Mo complex (3) converts to a bis(siloxy)acetylene complex (5) upon reduction and treatment with a silyl electrophile, Me₃SiCl. This process shows exclusive C–C coupling distinct from the previously reported phenylene-linked analogue that undergoes C–O cleavage. Further CO catenation can be engendered from 5 under mild conditions providing metallacyclobutenone complex 6, with a C₃O₃ organic motif derived from CO. Differences in reactivity are assigned to the nature of the arene linker, where the naphthalenediyl fragment shows a propensity for η⁴ binding previously not observed for phenylene. Consistent with this hypothesis, a Mo precursor with a 1,3-cyclohexadienediyl-based linker was prepared which also showed exclusive formation of a bis(siloxy)acetylene complex and subsequent coupling of a third CO molecule.

Item Type:Article
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URLURL TypeDescription
Low, Choon Heng0000-0002-9219-3377
Buss, Joshua A.0000-0002-3347-8583
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2022 American Chemical Society. Received: January 24, 2022; Published: May 9, 2022. We are grateful to the NSF (CHE-1800501 to T.A.; GRFP to J.A.B.) and the Agency of Science, Technology and Research (A*STAR), Singapore (C.H.L.) for funding. We thank Lawrence M. Henling and Michael K. Takase for crystallographic assistance and David VanderVelde for advice on NMR spectroscopy. The Dow Next Generation Educator Fund is thanked for instrument grants to Caltech. The authors declare no competing financial interest. Accession Codes. CCDC 1495764, 1909081–1909084, and 2117715–2117716 contain the supplementary crystallographic data for this paper
Funding AgencyGrant Number
Agency for Science, Technology and Research (A*STAR)UNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
Subject Keywords:Aromatic compounds, Hydrocarbons, Ligands ,Organophosphorus compounds, Reactivity
Issue or Number:20
Record Number:CaltechAUTHORS:20220520-231441000
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Official Citation:Molybdenum-Mediated Coupling of Carbon Monoxide to a C3 Product on a Single Metal Site. Choon Heng Low, Joshua A. Buss, and Theodor Agapie. Inorganic Chemistry 2022 61 (20), 7710-7714; DOI: 10.1021/acs.inorgchem.2c00266
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114851
Deposited By: George Porter
Deposited On:24 May 2022 18:10
Last Modified:01 Jun 2022 17:01

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