The sign of the 57Fe quadrupole splittings in iron(II) low-spin compounds: partial quadrupole splittings and bonding properties of ligands

Abstract
The signs of Vzz(and e2qQ) at the 57Fe nucleus for the following compounds have been measured by use of the Mössbauer magnetic field technique: trans-FeCl2(p-MeO·C6H4·NC)4, trans-FeCl2(depe)2[depe = 1,2-bis(diethylphosphino)ethane]. Na3[Fe(CN)5NH3],H2O, K3[Fe(CN)5H2O],7H2O, all positive; cis-FeCl2(p-MeO·C6H4·NC)4 and trans-Fe(CN)2(EtNC)4, both negative. The 2: –1 trans:cis ratio has been confirmed, and partial quadrupole splittings (p.q.s.) for sixteen ligands have been assigned. These p.q.s. values become more positive as the π-acceptor function of a ligand increase, and the σ-donor properties of a ligand decreases [i.e. p.q.s.α(πσ)]. The p.q.s. values are related to the bonding properties of these ligands.

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