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• W2734636268 endingPage "8828" @default.
• W2734636268 startingPage "8817" @default.
• W2734636268 abstract "Seven [FeL2][BF4]2 complex salts were prepared, where L is a 6-substituted 2,4-di(pyrazol-1-yl)-1,3,5-triazine (bpt) derivative. The complexes are all crystallographically high-spin, and exhibit significant distortions from an ideal D2d-symmetric coordination geometry. In one case, an unusual type of metal ion disorder was observed among a cubic array of ligands in the crystal lattice. The complexes are also high-spin between 3 and 300 K in the solid state and, where measured, between 239 and 333 K in CD3CN solution. This result is unexpected, since homoleptic iron(II) complexes of related 2,6-di(pyrazol-1-yl)pyridine, 2,6-di(pyrazol-1-yl)pyrazine, and 2,6-di(pyrazol-1-yl)pyrimidine derivatives often exhibit thermal spin-crossover behavior. Gas-phase density functional theory calculations confirm the high-spin form of [Fe(bpt)2]2+ and its derivatives is stabilized relative to iron(II) complexes of the other ligand types. This reflects a weaker Fe/pyrazolyl σ-bonding interaction, which we attribute to a small narrowing of the chelate ligand bite angle associated with the geometry of the 1,3,5-triazinyl ring. Hence, the high-spin state of [Fe(bpt)2]2+ centers does not reflect the electronic properties of its heterocyclic ligand donors but is imposed by the bpt ligand conformation. A high-spin homoleptic iron(III) complex of one of the bpt derivatives was also synthesized." @default.
• W2734636268 created "2017-07-21" @default.
• W2734636268 creator A5046395431 @default.
• W2734636268 creator A5055884135 @default.
• W2734636268 creator A5082064812 @default.
• W2734636268 date "2017-07-12" @default.
• W2734636268 modified "2023-10-15" @default.
• W2734636268 title "Iron(II) Complexes of 2,4-Dipyrazolyl-1,3,5-triazine Derivatives—The Influence of Ligand Geometry on Metal Ion Spin State" @default.
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