American Chemical Society
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Ene Reactivity of an FeNR Bond Enables the Catalytic α‑Deuteration of Nitriles and Alkynes

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journal contribution
posted on 2022-09-07, 19:09 authored by Yafei Gao, Maren Pink, Veronica Carta, Jeremy M. Smith
Herein, we report the reactions of an Fe(II) imido complex [Ph2B(tBuIm)2FeNDipp] (1) with internal alkynes and isobutyronitrile, affording the Fe amido allenyl complexes [Ph2B(tBuIm)2Fe(NHDipp)((R1)CCC(R2)(H))] (R1 = Et or nPr; R2 = Me or Et, 2–5) and the Fe amido keteniminate complex [Ph2B(tBuIm)2Fe(NHDipp)(NCCMe2)K(THF)]n (8-K), respectively. These transformations represent the previously unknown ene-like reactivity of a metal–ligand multiple bond. Stoichiometric reactions of 2 and 8-K with DippNH2 lead to the regeneration of 3-hexyne and isobutyronitrile, respectively, with concomitant formation of the bis(anilido) complex [Ph2B(tBuIm)2Fe(NHDipp)2] (9). These results provide the platform for 1 as an efficient catalyst for the selective α-deuteration of nitriles and alkynes by RND2. These results demonstrate a new reaction mode for metal imido complexes and suggest new avenues for using the imido ligand in catalysis.