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.