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Hydrodeoxygenative Cyclotetramerization of Carbon Monoxide by a Trinuclear Titanium Polyhydride Complex

  • Shaowei Hu
    Shaowei Hu
    Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    More by Shaowei Hu
  • Takanori Shima
    Takanori Shima
    Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
  • , and 
  • Zhaomin Hou*
    Zhaomin Hou
    Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
    *Email: [email protected]
    More by Zhaomin Hou
Cite this: J. Am. Chem. Soc. 2020, 142, 47, 19889–19894
Publication Date (Web):November 10, 2020
https://doi.org/10.1021/jacs.0c10403
Copyright © 2020 American Chemical Society

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    Abstract

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    The reductive coupling of carbon monoxide (CO) by metal hydrides is of fundamental interest and practical importance. Herein we report an unprecedented hydrodeoxygenative cyclotetramerization of CO by a trinuclear titanium polyhydride complex [(C5Me4SiMe3)Ti]33-H)(μ2-H)6 (1). The reaction of CO with 1 at −78 °C gave an ethen-1,2-diyl species [CH═CH]2– through the hydrodeoxygenative dimerization of two molecules of CO, which upon cycloaddition to another two molecules of CO afforded a cyclobuten-3,4-diyl-1,2-diolate unit [C4H2O2]4–. The hydrogenolysis of the [C4H2O2]4– species with H2 yielded a tetrahydrocyclobuten-1,2-diolate species [C4H4O2]2–, which on heating at 100 °C gave a cyclobuten-2-yl-1-olate product [C4H4O]2–. The acidolysis of the [C4H2O2]4– and [C4H4O]2– species with HCl afforded γ-butyrolactone and cyclobutanone, respectively.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c10403.

    • Syntheses and characterization, NMR spectra, crystallographic data for 25, synthetic and spectroscopic details (PDF)

    • Crystallographic data for 2 (CCDC 1858997) (CIF)

    • Crystallographic data for 3 (CCDC 1858998) (CIF)

    • Crystallographic data for 4 (CCDC 1858999) (CIF)

    • Crystallographic data for 5 (CCDC 2032847) (CIF)

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