A DFT study was initiated to map the basicity of 111 metal nitride complexes of 3d and 4d metals: V, Cr, Mn, Mo, Tc and Ru. All complexes were gathered from the Cambridge Structural Database and have a single terminal nitride ligand. The levels of theory evaluated were B3LYP/def2-svp and B3LYP/6-311+G(d,p) with a SMD-acetonitrile continuum solvation model for both. Protonation of the metal-nitride complex resulted in the formation of a conjugate base (a cationic metal-imide). From the free energy of this protonation, the pKb(MN) was calculated to assess the effects of metal identity, ligands, oxidation state, and conjugate base stabilization upon nitride basicity. In general, the basicity of the N–H bonds of transition metal-nitride complexes decreases from left to right across the 3d and 4d rows while it increases from 3d to 4d nitrides. Factors affecting the range in pKb(MN) for each metal are discussed.

Mapping basicity of 3d and 4d metal nitrides: A DFT study

ACS Spring Meeting 2021

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