Theoretical investigation of tetrahedral distortion of four-coordinate iron(II) centres in FePd(CN)4.

ABSTRACT

The tetrahedral distortion of iron(ii) centres in the cyanide-bridged framework FePd(CN)4 was recently demonstrated experimentally. Here, we theoretically confirmed the electronically driven tetrahedral distortion of iron(ii) by comparing the density of states and total energies of FePd(CN)4 (d6) and ZnPd(CN)4 (d10). The calculation results suggested that a Jahn-Teller-like effect is caused on the tetrahedral geometry by the electronic effect of unequally occupied non-bonding 3d orbitals in the corresponding structure.