Hydrogen atom abstraction (HAA) from 1,4-cyclohexadiene (CD-H) by (dtbpe)Ni(NAr) to form a Nil-amide, (dtbpe)Ni(NHAr), and cyclohexadienyl radical is calculated to be thermodynamically reasonable, Delta H-HAA(dtbpe) = -1.3 kcal/mol, dtbpe = bis(di-tert-butylphosphino)ethane, Ar = 2,6-diisopropylphenyl. However, radical rebound to form a metal-bound amine is highly endothermic (Delta H-reb(dtbpe) = +25.1 kcal/mol). Analysis of bond enthalpies indicates that weakening of the Ni-N bond (Ni-amide -> Ni-amine) upon radical rebound is not compensated by the weak C-N bond formed. Hence, a ligand was sought that would enhance the metal-amine bond strength while diminishing the metal-amide bond strength. Reaction of (dfmpe)Ni(NAr) with CD-H was thus analyzed, dfmpe = bis(di(trifluoromethyl)phosphino)ethane. While there is a small change in the thermodynamics of HAA (Delta H-HAA(dfmpe) = -5.7 kcal/mol), there is a profound change in the rebound step (Delta H-reb(dfmpe) = -7.8 kcal/mol) upon replacing dtbpe by dfmpe. Regeneration of the nitrene active species by reaction of ArN3 with the metal-bound product is calculated to be highly exothermic, Delta H-reg = -36.7 kcal/mol. Two candidates for a precatalyst, (dfmpe)Ni(COD) and (dfmpe)Ni(bpy), COD = 1,5-cyclooctadiene and bpy = 2,2'-bipyridine, were calculated to undergo highly exothermic reactions with ArN3 to form the nitrene active species. The calculated enthalpic barrier for HAA of CD-H by (dfmpe)Ni(NAr) is 21.3 kcal/mol. Hence, consideration of the computed thermodynamics and kinetics suggests that nickel-nitrenes with fluorinated phosphine supporting ligation are promising candidates for catalytic amination of C-H bonds.