In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2014, No. 22 ( 2014-08), p. 3587-3599
Abstract:
A biomimetic mononuclear iron(III) model complex was investigated in detail by density functional theory (DFT) calculations. Structural and energetic criteria were employed to confirm the S = 3/2 intermediate state to be the ground state. The ground state was verified by using both pure and hybrid functionals with different amounts of exact Hartree–Fock exchange. A comprehensive study of the influence of the functional as well as thermodynamic corrections to the energetic ordering of spin states was performed. A modified B3LYP functional with 10 % Hartree–Fock exchange was able to reproduce the structural properties in excellent agreement with the experimental data. The thermodynamics of two possible spin‐crossover transitions [intermediate‐spin to high‐spin (IS–HS) and low‐spin to high‐spin (LS–HS)] were investigated. A torsional profile obtained by rotation of the axial ligand revealed a spin‐dependent preference of the ligand orientation. The structure solved by X‐ray crystallography corresponds to the global energetic minimum of the complex in the S = 3/2 and 5/2 states but not in the S = 1/2 state. This study demonstrates that the spin multiplicity affects not only the structural properties but may also influence the chemical reactivity of this transition metal complex in general.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2014.22
DOI:
10.1002/ejic.201402295
Language:
English
Publisher:
Wiley
Publication Date:
2014
detail.hit.zdb_id:
1475009-0
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