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Preparation of 6-aminocyclohepta-2,4-dien-1-one Derivatives via Tricarbonyl(tropone)iron
Published on: August 12, 2019
An unprecedented trinuclear structure involving two high-spin and one spin-crossover iron(II) centers
George Psomas1, Nicolas Bréfuel, Françoise Dahan
1Laboratoire de Chimie de Coordination, UPR CNRS 8241, 205 route de Narbonne, 31077 Toulouse Cedex 04, France.
Abstract:
Anaerobic reaction of ferrous thiocyanate with the deprotonated form of the pentadentate dinucleating Schiff base 1,3-bis[(2-pyridylmethyl)imino]propan-2-ol (LH) yields the novel trinuclear [Fe3L2(NCS)4(H2O)] species 1. LH results from the bis-condensation of 2-acetyl-pyridine with 1,3-diaminopropan-2-ol and includes an N4O donor set. The X-ray crystal structure of 1 [C38H40N12O3S4Fe3, triclinic, space group P-1; a = 10.7730(10) angstroms, b = 12.2048(14) angstroms, c = 19.0559(19) angstroms, alpha = 76.908(12) degrees, beta = 89.106(12) degrees, gamma = 79.637(12) degrees, V = 2399.8(4) angstroms3] can be described either as a bent linear arrangement of ferrous centers pairwise bridged through the alkoxo oxygen atom of L- or as a triangular FeII3 core with an Fe2-SCN-Fe3 bridge as the longer side of the Fe1-Fe2-Fe3 triangle. The metric parameters characterizing the ligand environments of the three ferrous centers in 1 and its Mössbauer spectra show that this unprecedented trinuclear structure involves two high-spin (Fe2 and Fe3) and one spin-crossover (Fe1) FeII centers. The donor set to the spin-crossover center (Fe1) is unprecedented: two Npyridine, two Nimine, and two Oalkoxo. Weak antiferromagnetic interactions transmitted through the end-to-end NCS bridge and/or through the O1-Fe1-O2 bridge operate between Fe2 and Fe3.
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