Related Experiment Video
Updated: Dec 25, 2025
Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Assembly of High-Spin [Fe3] Clusters by Ligand-Based Multielectron Reduction
Davide Toniolo1, Rosario Scopelliti1, Ivica Zivkovic2
1Insititut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Abstract:
The hexanuclear [Na12Fe6(tris-cyclo-salophen)2(THF)14], 1-THF, and the trinuclear [Na6Fe3(tris-cyclo-salophen)(py)9], 1-py, Fe(II) clusters can be easily assembled in one step from the ligand-based reduction of the [FeII(salophen)(THF)] complex. These complexes consist of triangular cores where three Fe(II) ions are held together, within range of bonding interaction, by the hexa-amide, hexaphenolate macrocyclic ligand tris-cyclo-salophen. The tris-cyclo-salophen ligand is perfectly suited for binding three Fe(II) centers at short distances, allowing for strong magnetic coupling between the Fe(II) centers. The macrocyclic ligand is generated by the reductive coupling of the imino groups of three salophen ligands, resulting in three new C-C bonds. The six electrons stored in the ligand become available for the reduction of carbon dioxide with selective formation of carbonate.
More Related Videos
07:14Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
10:45Stable Aqueous Suspensions of Manganese Ferrite Clusters with Tunable Nanoscale Dimension and Composition
Published on: February 5, 2022
Related Concept Videos
02:42Valence Bond Theory
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
02:51Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
01:20Amides to Amines: LiAlH4 Reduction
Amide reduction requires two equivalents of the reducing agent, acting as a source of hydride ions. As shown in the figure, the reaction is initiated with a nucleophilic attack by the hydride ion at the carbonyl carbon to form a tetrahedral intermediate.
01:19Acid Halides to Alcohols: LiAlH4 Reduction
The mechanism proceeds in three steps. First, the nucleophilic hydride ion attacks the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs as a leaving group, generating an aldehyde. A second nucleophilic attack by the hydride yields an alkoxide ion, which, upon protonation, gives a primary alcohol as...