Tuning Electronic Structure To Control Manganese Nitride Activation

Investigation of a series of oxidized nitridomanganese­(V) salen complexes with different para ring substituents (R = CF₃, tBu, and NMe₂) demonstrates that nitride activation is dictated by remote ligand electronics. For R = CF₃ and tBu, oxidation affords a Mn­(VI) species and nitride activation, with dinitrogen homocoupling accelerated by the more electron-withdrawing CF₃ substituent. Employing an electron-donating substituent (R = NMe₂) results in a localized ligand radical species that is resistant to N coupling of the nitrides and is stable in solution at both 195 and 298 K