posted on 2022-09-07, 19:09authored byYafei Gao, Maren Pink, Veronica Carta, Jeremy M. Smith
Herein,
we report the reactions of an
Fe(II) imido complex [Ph2B(tBuIm)2FeNDipp]− (1) with internal alkynes and isobutyronitrile, affording the Fe amido
allenyl complexes [Ph2B(tBuIm)2Fe(NHDipp)((R1)CCC(R2)(H))]− (R1 = Et or nPr; R2 = Me or Et, 2–5) and
the Fe amido keteniminate complex [Ph2B(tBuIm)2Fe(NHDipp)(NCCMe2)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.