Published in the Journal of the American Chemical Society (JACS), Direct Comparison of C−H Bond Amination Efficacy through Manipulation of Nitrogen-Valence Centered Redox: Imido versus Iminyl adds to the Betley Group's latest investigations.
Introduction:
"Late transition metal complexes featuring metal−ligand multiple bonds are investigated intensely to probe their efficacy for functional group transfer to organic substrates. Within this class of coordination complexes, iron complexes to which the nitrene functional group (R−N) is bound have now been characterized spanning a large range of oxidation states and electronic structures (FeII S = 0;16 FeIII S = 1 /2, S = 3 /2, 17−23 S = 5 /2; 24 FeIII(• NR) S = 2;25,26 FeIV S = 0, S = 1;27−31 FeV S = 1 /2 32,33). Of these examples, only the high-spin, ferric imido and iminyl complexes have been demonstrated to be competent for nitrene group transfer into aliphatic or olefinic substrates. The unique electronic configuration of the two amination agents warrants further investigation into how the electronic structure of the reactive intermediate impacts functional group transfer from complexes bearing metal−ligand multiple bonds."
