Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
J Am Chem Soc. 2022 Sep 21;144(37):17165-17172. doi: 10.1021/jacs.2c07462. Epub 2022 Sep 7.
Herein, we report the reactions of an Fe(II) imido complex [PhB(BuIm)Fe═NDipp] () with internal alkynes and isobutyronitrile, affording the Fe amido allenyl complexes [PhB(BuIm)Fe(NHDipp)((R)C═C═C(R)(H))] (R = Et or Pr; R = Me or Et, ) and the Fe amido keteniminate complex [PhB(BuIm)Fe(NHDipp)(N═C═CMe)K(THF)] (), respectively. These transformations represent the previously unknown ene-like reactivity of a metal-ligand multiple bond. Stoichiometric reactions of and with DippNH lead to the regeneration of 3-hexyne and isobutyronitrile, respectively, with concomitant formation of the bis(anilido) complex [PhB(BuIm)Fe(NHDipp)] (). These results provide the platform for as an efficient catalyst for the selective α-deuteration of nitriles and alkynes by RND. These results demonstrate a new reaction mode for metal imido complexes and suggest new avenues for using the imido ligand in catalysis.
在此，我们报告了一个 Fe(II)亚氨基配合物 [PhB(BuIm)Fe═NDipp]（）与内部炔烃和异丁腈的反应，得到了 Fe 酰胺烯丙基配合物 [PhB(BuIm)Fe(NHDipp)((R)C═C═C(R)(H))]（R = Et 或 Pr；R = Me 或 Et，）和 Fe 酰胺烯酮亚胺配合物 [PhB(BuIm)Fe(NHDipp)(N═C═CMe)K(THF)]（）。这些转化代表了金属配体多重键以前未知的类似 Ene 的反应性。和 与 DippNH 的化学计量反应分别导致 3-己炔和异丁腈的再生，同时形成双（苯胺基）配合物 [PhB(BuIm)Fe(NHDipp)]（）。这些结果为通过 RND 选择性α-氘化腈和炔烃提供了作为有效催化剂的平台。这些结果证明了金属亚氨基配合物的一种新反应模式，并为在催化中使用亚氨基配体提供了新途径。
