Role of "S" Substitution on C-H Activation Reactivity of Iron(IV)-Oxo Cyclam Complexes: a Computational Investigation.

A comprehensive density functional theory (DFT) investigation has been presented in this article to address the role of equatorial sulfur ligation in C-H activation. A non-heme iron-oxo compound with four nitrogen atoms constituting the equatorially connected macrocyclic framework (represented as N) [Fe(IV)═O(THC)(CHCN)](THC = 1,4,8,11-tetrahydro1,4,8,11-tetraazacyclotetradecane) has been considered as the base compound. Other complexes have been anticipated by the sequential replacement of this nitrogen by sulfur, that is, N, NS, NS, NS, and S. Counterions, as always, have been considered to avoid the self-interaction error in DFT. Generally, the anti-conformers (with respect to equatorial N-H and Fe═O) turned out to be the most stable. It was found that with the enrichment of the equatorial sulfur atom, reactivity increases successively, that is, we get the trend N < NS < NS < NS < S Our investigations have also verified the available experimental results where it has been reported that NS is more reactive than N in their mixed conformation. In search of insights into this typical pattern of reactivity, the interplay of several factors has been recognized, such as the distortion energy which decreases for the transition states with the addition of sulfur; the spin density on the oxygen atom which increases implying that the radical character of abstractor increases on sulfur ligation; the energy of the electron acceptor orbital (the lowest unoccupied molecular orbital (σ*)) which decreases continuously with the sulfur substitution; and the triplet-quintet oxidant energy gap which decreases consistently with S enrichment in the equatorial position. The computational predictions reported here, if further validated by experiments, will definitely encourage the synthesis of sulfur-ligated bio-inspired complexes instead of the ones constituting nitrogen exclusively.