Oxidative Addition of the Carbon-Hydrogen Bond Is Not the Rate-Determining Step in the Remote Functionalization of Nitriles by Bare Fe(I) Ions

Article abstract of DOI:10.1021/ja00195a004

The study of D-labeled 5-cyanononane isotopomers in the gas phase provides evidence that the Fe⁺-mediated remote functionalization of nitriles, resulting in the regiospecific generation of H2 and C2H4 from the ω and (ω - 1) position of the alkyl chain, can be described as follows: (i) Oxidative addition of a methyl C-H bond is not rate limiting.For the generation of C2H(4-x)Dx it is the elimination of the olefin which is associated with kinetic isotope effects comparable to the ones reported earlier for other systems. (ii) The generation of H(2-x)Dx is affected bytwo isotope effects.One concerns the β-hydrogen transfer (k_H/k_D = 1.59) and the other the reductive elimination of hydrogen (k_H2/k_HD = 1.70 and k_HD/k_D2 = 1.44).