Density Functional Theory of the Iron-Nitrosyl (S=3/2) Complex

摘要

On the basis of density functional theory (DFT),the iron-nitrosyl complex Fe[Me_3TACN](NO)(N_3)_2 (S=3/2) is studied via the B3LYP hybrid method.Its Raman vibrational frequencies,atomic net charges,and spin densities are analyzed.The related complexes Fe(NH_3)_6~(n+) (n=1,2,and 3) are employed as reference compounds to determine the characteristics of the central iron.Our results indicate that the S=3/2 spin ground state of Fe[Me_3TACN](NO)(N_3)_2 is best described by the presence of Fe~(II) (S=2) anti-ferromagnetically coupled to NO~0 (S=1/2) yielding Fe~(II)[Me_3TACN](NO~0)(N_3~-)_2.This is clearly different from the previous Fe~(III)-NO~-theoretical assignment.