A Unified Treatment of the Relationship between Ligand Substituents and Spin State in a Family of Iron(II) Complexes

The influence of ligands on the spin state of a metal ion is of central importance for bioinorganic chemistry, and the production of base-metal catalysts for synthesis applications. Complexes derived from [Fe(bpp)₂]²⁺ (bpp=2,6-di{pyrazol-1-yl}pyridine) can be high-spin, low-spin, or spin-crossover (SCO) active depending on the ligand substituents. Plots of the SCO midpoint temperature (T1/2) in solution vs. the relevant Hammett parameter show that the low-spin state of the complex is stabilized by electron-withdrawing pyridyl ("X") substituents, but also by electron-donating pyrazolyl ("Y") substituents. Moreover, when a subset of complexes with halogeno X or Y substituents is considered, the two sets of compounds instead show identical trends of a small reduction in T1/2 for increasing substituent electronegativity. DFT calculations reproduce these disparate trends, which arise from competing influences of pyridyl and pyrazolyl ligand substituents on Fe-L σ and π bonding. Highs and lows: The low-spin state of the complex shown is stabilized by electron-withdrawing pyridyl "X" substituents, but also by electron-donating pyrazolyl "Y" substituents. DFT calculations reproduce these results, which arise from competing influences of pyridyl and pyrazolyl ligand substituents on Fe-L σ and π bonding.