Influence of polyoxometalate ligands on the nature of high-valent transition metal nitrido species. A theoretical analysis of experimentally known and unprecedented compounds

Abstract

The electronic structure of group 6–8 transition metal (TM) nitrido derivatives [PW₁₁O₃₉{TM^VIN}]⁴⁻ is studied computationally and the potential reactivity of the polyoxoanions is discussed. The observed electrophilic reactivity for the Ru^VI nitrido derivative is rationalized from frontier molecular orbital analysis. When we move to the left or down in the periodic table (TM = Os, Tc, Re, Mo and W) the electrophilic character of the polyoxometalate decreases or the cluster should be better regarded as a nucleophile. The DFT analysis of the redox properties suggests that the still unknown high-valent Mn^VIN and Fe^VIN units could be stabilized by the porphyrin-like ligand [PW₁₁O₃₉]⁷⁻ and their electronic structure indicates that these anions should have a high potential reactivity towards nucleophiles.