Influence of the electronic effect of an ancillary ligand on MMCT and LMCT in localized cyanide-bridged complexes containing non-innocent ligands

Abstract

Mixed-valence (MV) complexes containing non-innocent ligands are excellent models for the investigation of the electron-transfer process. A series of twelve bimetallic cyanide-bridged complexes [CpMen(dppe)RuCNFeLx][A](A = PF6- or I-, CpMen =...

Coexistence of Three Different Spin States in a Cyanido‐Bridged Trinuclear Iron(III) Complex with an Unusual FeIII to Ligand Charge Transfer

“…Obviously, the electron density assignment of 1[PF 6 ] is predominately delocalized over the [Fe III (L⋅ N4 )] − fragment and only small spin density distribution is resident on the CpMe 3 Fe(dppe)CN fragment. It is notable that, the spin density distribution on the Fe III (2.549) and (L⋅ N4 ) 2− (−0.684) supports that fact that the unpaired electrons are 3 and 1 with the opposite spin direction [18] . These calculation results in cooperation with various experimental measurements provide momentous evidences on the investigation about electronic structures and electron transfer of cyanido‐bridged complexes containing redox ligands of non‐innocent and innocent ways.…”

“…It is notable that, the spin density distribution on the Fe III (2.549) and (L * N4 ) 2À (À 0.684) supports that fact that the unpaired electrons are 3 and 1 with the opposite spin direction. [18] These calculation results in cooperation with various experimental measurements provide momentous evidences on the investigation about electronic structures and electron transfer of cyanido-bridged complexes containing redox ligands of non-innocent and innocent ways. N4 was oxidized into the innocent ligand (L OX N4 ) À which possesses a strong electron-accepting ability, and the iron center in the [Fe III (L N4 )] changes from the five-coordinated Fe III with the intermediatespin (S = 3/2) to the six-coordinated Fe III with the low-spin (S = 1/2).…”