Untangling ancillary ligand donation versus locus of oxidation effects on metal nitride reactivity.

We detail the relative role of ancillary ligand electron-donating ability in comparison to the locus of oxidation (either metal or ligand) on the electrophilic reactivity of a series of oxidized Mn salen nitride complexes. The electron-donating ability of the ancillary salen ligand was tuned via the para -phenolate substituent (R = CF 3 , H, t Bu, O i Pr, NMe 2 , NEt 2 ) in order to have minimal effect on the geometry at the metal center. Through a suite of experimental (electrochemistry, electron paramagnetic resonance spectroscopy, UV-vis-NIR spectroscopy) and theoretical (density functional theory) techniques, we have demonstrated that metal-based oxidation to [Mn VI (Sal R )N] + occurs for R = CF 3 , H, t Bu, O i Pr, while ligand radical formation to [Mn V (Sal R )N] + ˙ occurs with the more electron-donating substituents R = NMe 2 , NEt 2 . We next investigated the reactivity of the electrophilic nitride with triarylphosphines to form a Mn IV phosphoraneiminato adduct and determined that the rate of reaction decreases as the electron-donating ability of the salen para -phenolate substituent is increased. Using a Hammett plot, we find a break in the Hammett relation between R = O i Pr and R = NMe 2 , without a change in mechanism, consistent with the locus of oxidation exhibiting a dominant effect on nitride reactivity, and not the overall donating ability of the ancillary salen ligand. This work differentiates between the subtle and interconnected effects of ancillary ligand electron-donating ability, and locus of oxidation, on electrophilic nitride reactivity.