4.8 Article

Distinct Reactivity Modes of a Copper Hydride Enabled by an Intramolecular Lewis Acid

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 33, 页码 15038-15046

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AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c02937

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  1. NIGMS of the NIH
  2. NSF [1R35GM136360-01]
  3. [CHE 1625543]

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Researchers disclosed a ligand with an appended boron Lewis acid and successfully synthesized a series of tetrahedral complexes, including a boron-capped cuprous hydride, by metalation with Cu(I). Different reactivity modes were demonstrated depending on the chemical oxidation state, including hydride transfer to CO2 in the copper(I) state, oxidant-induced H2 evolution, and alkyne reduction.
We disclose a 1,4,7-triazacyclononane (TACN) ligand featuring an appended boron Lewis acid. Metalation with Cu(I) affords a series of tetrahedral complexes including a boron-capped cuprous hydride. We demonstrate distinct reactivity modes as a function of chemical oxidation: hydride transfer to CO2 in the copper(I) state and oxidant-induced H2 evolution as well as alkyne reduction.

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