Ab Initio Ligand Field Molecular Mechanics and the Nature of Metal-Ligand π-Bonding in Fe(II) 2,6-di(pyrazol-1-yl)pyridine Spin Crossover Complexes

A ligand field molecular mechanics (LFMM) force field has been constructed for the spin states of [Fe(bpp)(2)](2+) (bpp=2,6-di(pyrazol-1-yl)pyridine) and related complexes. A new charge scheme is employed which interpolates between partial charges for neutral bpp and protonated [H(3)bpp](3+) to achieve a target metal charge. The LFMM angular overlap model (AOM) parameters are fitted to fully ab initio d orbital energies. However, several AOM parameter sets are possible. The ambiguity is resolved by calculating the Jahn-Teller distortion mode for high spin, which indicates that in [Fe(bpp)(2)](2+) pyridine is a pi-acceptor and pyrazole a weak pi-donor. The alternative fit, assumed previously, where both ligands act as pi-donors leads to an inconsistent distortion. LFMM optimisations in the presence of [BF4](-) or [PF6](-) anions are in good agreement with experiment and the model also correctly predicts the spin state energetics for 3-pyrazolyl substituents where the interactions are mainly steric. However, for 4-pyridyl or 4-pyrazolyl substituents, LFMM only treats the electrostatic contribution which, for the pyridyl substituents, generates a fair correlation with the spin crossover transition temperatures, T-1/2, but in the reverse sense to the dominant electronic effect. Thus, LFMM generates its smallest spin state energy difference for the substituent with the highest T-1/2. One parameter set for all substituted bpp ligands is insufficient and further LFMM development will be required.