Chromium Nitride Umpolung Tuned by the Locus of Oxidation

Oxidation of a series of Cr^V nitride salen complexes (CrNSal) with different para-phenolate substituents (R = CF₃, tBu, NMe₂) was investigated to determine how the locus of oxidation (either metal or ligand) dictates reactivity at the nitride. Para-phenolate substituents were chosen to provide maximum variation in the electron-donating ability of the tetradentate ligand at a site remote from the metal coordination sphere. We show that one-electron oxidation affords Cr^VI nitrides ([CrNSal]; R = CF₃, tBu) and a localized Cr^V nitride phenoxyl radical for the more electron-donating NMe₂ substituent ([CrNSal]). The facile nitride homocoupling observed for the Mn^VI analogues was significantly attenuated for the Cr^VI complexes due to a smaller increase in nitride character in the M≡N π* orbitals for Cr relative to Mn. Upon oxidation, both the calculated nitride natural population analysis (NPA) charge and energy of molecular orbitals associated with the {Cr≡N} unit change to a lesser extent for the Cr^V ligand radical derivative ([CrNSal]) in comparison to the Cr^VI derivatives ([CrNSal]; R = CF₃, tBu). As a result, [CrNSal] reacts with B(C₆F₅)₃, thus exhibiting similar nucleophilic reactivity to the neutral Cr^V nitride derivatives. In contrast, the Cr^VI derivatives ([CrNSal]; R = CF₃, tBu) act as electrophiles, displaying facile reactivity with PPh₃ and no reaction with B(C₆F₅)₃. Thus, while oxidation to the ligand radical does not change the reactivity profile, metal-based oxidation to Cr^VI results in umpolung, a switch from nucleophilic to electrophilic reactivity at the terminal nitride.