Effect of N-Methylation of Macrocyclic Amine Ligands on the Spin State of Iron(III): A Tale of Two Fluoro Complexes

Syntheses and characterization of [(cyclamacetate)FeF]PF6 (1) and the corresponding N-methylated complex
[(trimethylcyclamacetate)FeF]PF6 (3) are presented. Compound 1 is prepared in good yields from the analogous
chloro complex, whereas 3 is prepared by hydrolysis of the oxo-bridged diiron compound (Me3cyclam-acetate)Fe−O−FeCl3 (2) in the presence of PF6 anions. Magnetic susceptibility and spectroscopic data including electron
paramagnetic resonance and Mössbauer spectra indicate that 1 contains low-spin FeIII (S = 1/2), while 3 is high
spin (S = 5/2). Both octahedral fluoro complexes were investigated theoretically by density functional theory in
order to determine why the spin states of the two molecules are different. Energies calculated using the B3LYP
functional correctly predict 1 to have a low-spin S = 1/2 ground state and 3 to be high spin, regardless of whether
a solvation model is included. The difference between 1 and 3 is most likely a combination of steric effects caused
by the N-methyl groups, which compel the Fe−N bond distances to be longer in 3 than they ordinarily would be,
and also electronic effects, which cause the N-methylated ligand to be a weaker σ donor than its nonmethylated
counterpart.