Nitrene transfer reactions to various hydrocarbon molecules can be efficiently catalyzed by Fe complexes through a mechanism reminiscent of the oxygen transfer function of oxygenase enzymes. Such enzymes exhibit a high-valent iron oxo Fe(IV) = O as the active species, and it has also been proposed that an analogous species, i.e., Fe(IV) = NR (NR being the nitrene group) is responsible for the nitrene transfer activity. We describe here the influence of the Fe(IV) coordination sphere on some key parameters for nitrene transfer efficacy, such as the spin state of the Fe(IV) cation, the electronic affinity, and the bond dissociation energy of the NHR moiety. We explore here the electronic properties of Fe(IV) = NTs (NTs = tolylsulfonylimido group) mononuclear complexes with ligands involving phenolate and nitrogen donor groups, as catalytic properties with such ligands have been found to be quite promising. Six tetradentate ligands were studied, which derive from three different scaffolds: 2-methylenepyridine-N,N-bis(2-methylene-4,6-dichlorophenol) and 2-methylenepyridine-N,N-bis(2-methylene-4,6-dimethylphenol), N,N-dimethyl-N',N'-bis(2-methylene-4,6-dichlorophenol) ethylenediamine, and N,N-dimethyl-N',N'- bis(2-methylene-4,6-dimethylphenol) ethylenediamine, N,N'-bis(2-methylene-4,6-dichlorophenol)-N,N'-dimethyl-1,2-diaminoethane and N,N'-bis(2-methylene-4,6-dimethylphenol)-N,N'-dimethyl-1,2-diaminoethane. Thanks to thorough DFT computations, we present some rationalization of the electronic properties of the resulting Fe(IV) = NTs complexes in relation to their coordination sphere and compare them to other Fe(IV) nitrene active species. We show in particular the important role of the anionic character and strong π-donation of the phenolate groups.