Nucleophilic Aromatic Substitution in Hydrodefluorination Exemplified by Hydridoiridium(III) Complexes with Fluorinated Phenylsulfonyl-1,2-diphenylethylenediamine Ligands
作者:Asuka Matsunami、Yoshihito Kayaki、Shigeki Kuwata、Takao Ikariya
DOI:10.1021/acs.organomet.8b00242
日期:2018.6.25
family of iridium hydrides utilized as a hydrogen transfer catalyst is studied. Hydridoiridium(III) complexes bearing fluorinated phenylsulfonyl-1,2-diphenylethylenediamine ligands are spontaneously converted into iridacycles via selective C–F bond cleavage at the ortho position. NMR spectroscopic studies and synthesis of intermediate model compounds verify the stepwise pathway involving intramolecular
结合氟代芳烃的催化还原机理,研究了用作氢转移催化剂的氢化铱家族的分子内脱氟转化。带有氟化苯基磺酰基-1,2-二苯基乙二胺配体的氢化铱(III)配合物通过邻位的选择性CF键断裂自发地转变为iridacycles 。NMR光谱研究和中间模型化合物的合成验证了涉及邻位分子内取代的逐步途径-氢原子配体产生的氟原子,即加氢脱氟(HDF),以及随后在瞬态形成的C–H键处进行的氟化物辅助的环金属化。具有2,3,4,5,6-五氟苯基磺酰基(Fs)取代基的氢化铱络合物比具有2,3,4,5-四氟苯基磺酰基(Fs H)的类似物更容易受到HDF的影响。Fs H衍生物清楚地表明,CF键断裂优先于CH H活化而发生。这些实验结果坚定地支持了氢化铱分子在HDF中的亲核芳族取代(S N Ar)机制。