Ligand effects on hydrogen atom transfer from hydrocarbons to three-coordinate iron imides.
A new β-diketiminate ligand with 2,4,6-tri(phenyl)phenyl N-substituents provides protective bulk around the metal without exposing any weak C-H bonds. This ligand improves the stability of reactive iron(III) imido complexes with Fe═NAd and Fe═NMes functional groups (Ad = 1-adamantyl; Mes = mesityl). The new ligand gives iron(III) imido complexes that are significantly more reactive toward 1,4-cyclohexadiene than the previously reported 2,6-diisopropylphenyl diketiminate variants. Analysis of X-ray crystal structures implicates Fe═N-C bending, a longer Fe═N bond, and greater access to the metal as potential reasons for the increase in C-H bond activation rates.
Department of Chemistry, University of Rochester, Rochester, New York 14627, United States.
Ryan E
RE
Cowley
Patrick L
PL
Holland