Ene Reactivity of an Fe=NR Bond Enables the Catalytic α-Deuteration of Nitriles and Alkynes

Gao, Yafei; Pink, Maren; Carta, Veronica; Smith, Jeremy M.

doi:10.1021/jacs.2c07462

Ene Reactivity of an Fe=NR Bond Enables the Catalytic α-Deuteration of Nitriles and Alkynes

Journal Article · Wed Sep 07 00:00:00 EDT 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c07462· OSTI ID:1903363

^[1]; ^[2]; Carta, Veronica ^[2]; ^[2]

Indiana Univ., Bloomington, IN (United States); Indiana University
Indiana Univ., Bloomington, IN (United States)

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. Furthermore, these results demonstrate a new reaction mode for metal imido complexes and suggest new avenues for using the imido ligand in catalysis.

View Accepted Manuscript (DOE)

Research Organization:: Indiana Univ., Bloomington, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019466

OSTI ID:: 1903363

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 37 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Ene Reactivity of an Fe=NR Bond Enables the Catalytic α-Deuteration of Nitriles and Alkynes

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