Site preferences in hetero-metallic [Fe_9-xNi_x] clusters: a combined crystallographic, spectroscopic and theoretical...

The reaction of mixtures of Fe(O₂CMe)₂·2H₂O and Ni(O₂CMe)₂·4H₂O of various compositions with di-2-pyridyl ketone (py₂CO, dpk) in MeCN under an inert atmosphere afforded a family of hetero-metallic enneanuclear clusters with general formula [Fe_9-xNi_x(μ₄-OH)₂(O₂CMe)₈(py₂CO₂)₄] (2, x = 1.00; 3: x = 6.02; 4, x = 7.46; 5, x = 7.81). Clusters 2-5 are isomorphous to the homo-metallic [Fe₉] cluster (1) previously reported by some of us, and also isostructural to the known homo-metallic [Ni₉] cluster. All four clusters contain a central M^II ion in an unusual 8-coordinate site and eight peripheral M^II ions in distorted octahedral environments. The distribution of Fe^II and Ni^II ions over these two distinct coordination sites in 2-5 can be established through a combination of X-ray fluorescence and Mössbauer spectroscopies, which show that Fe^II preferentially occupies the unique 8-coordinate metal site while Ni^II accumulates in the octahedral holes. Density functional theory indicates that the distribution of ions across the two sites arises not from any intrinsic preference of the Fe^II ions for the 8-coordinate sites, but rather because of the large ligand field stabilization energy available to Ni^II in octahedral coordination.