Fluorocarbons Modulate the Coordination Sphere of f‐Element Complexes

Álvarez, Santiago; Menjón, Babil

doi:10.1002/anie.201310916

Cited by 7 publications

(5 citation statements)

References 24 publications

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“…The uranyl group, UO 2 2+ is ubiquitous in the chemistry of uranium (VI), but UO double bonds also exist in uranium compounds with lower oxidation states. The uranium atoms adopt a variety of coordination numbers and coordination geometries, including ill-defined coordination numbers and geometries along polyhedral interconversion paths . Those characteristics make the uranium complexes in general an ideal case for the use of normalized polyhedra, a study that can also be applied to other actinides.…”

Section: Distortions Of Coordination Polyhedra Due To Multiple Bondingmentioning

confidence: 99%

Stereochemistry of Complexes with Double and Triple Metal–Ligand Bonds: A Continuous Shape Measures Analysis

Álvarez¹,

Menjón

Falceto³

et al. 2014

Inorg. Chem.

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To each coordination polyhedron we can associate a normalized coordination polyhedron that retains the angular orientation of the central atom-ligand bonds but has all the vertices at the same distance from the center. The use of shape measures of these normalized coordination polyhedra provides a simple and efficient way of discriminating angular and bond distance distortions from an ideal polyhedron. In this paper we explore the applications of such an approach to analyses of several stereochemical problems. Among others, we discuss how to discern the off-center displacement of the metal from metal-ligand bond shortening distortions in families of square planar biscarbene and octahedral dioxo complexes. The normalized polyhedron approach is also shown to be very useful to understand stereochemical trends with the help of shape maps, minimal distortion pathways, and ligand association/dissociation pathways, illustrated by the Berry and anti Berry distortions of triple-bonded [X≡ML4] complexes, the square pyramidal geometries of Mo coordination polyhedra in oxido-reductases, the coordination geometries of actinyl complexes, and the tetrahedricity of heavy atom-substituted carbon centers.

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Section: Distortions Of Coordination Polyhedra Due To Multiple Bondingmentioning

confidence: 99%

Stereochemistry of Complexes with Double and Triple Metal–Ligand Bonds: A Continuous Shape Measures Analysis

Álvarez¹,

Menjón

Falceto³

et al. 2014

Inorg. Chem.

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“…4). 44 An additional feature often associated with C-F→Ln interactions is π-stacking of electron deficient aryl rings. Favorable arene interactions have been observed in a parallel displaced fashion for pentafluorophenyl rings between ligands.…”

Section: Modulation Of Molecular Geometriesmentioning

confidence: 99%

C–F→Ln/An interactions in synthetic f-element chemistry

2016

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The coordination of C-F moieties to electrophilic metal cations has been increasingly recognized in f-element chemistry over the last two decades. These C-F→Ln/An interactions are readily identified in the solid state and can persist in solution. The binding energies of C-F→Ln/An interactions lead to their ready displacement to expose metal centers to substrates, which is implicated in cationic polymerization catalysts. C-F→Ln/An coordination is also an elementary step in C-F bond activation, proceeding through either homolytic or heterolytic cleavage of chemically inert C-F bonds. The influence of C-F→Ln/An interactions on the geometries of coordination compounds and their electronic impact on metal cations are also examined in this Perspective article.

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“…For example, the average Ce–F bond enthalpy of CeF 3 (g) is 153 kcal/mol, comparable to the bond enthalpy of the C 6 F 5 –F bond at 154 kcal/mol . Second, in spite of the fact that the fluorine atom is not a particularly good Lewis donor or hydrogen bond acceptor, lanthanides and actinides form significant interactions with C–F bonds either intermolecularly or intramolecularly. − While the former guarantees that the C–F bond transformation is thermodynamically favorable, the latter allows a relatively low activation barrier for C–F activation.…”

Section: Introductionmentioning

confidence: 99%

Aromatic C–F Bond Activation by Rare-Earth-Metal Complexes

Huang

Diaconescu

2016

Organometallics

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C-F bond activation is a challenging reaction with increasing importance in synthesis. The strength of the C-F bond and the shielding effect of the fluorine atom render its activation difficult. Rare-earth metals offer an exceptional opportunity for this process because the high dissociation energy of the M-F bond offsets the strength of the C-F bond. Herein we report a unique reaction for the C-F activation of aromatic bonds by rare-earth metal complexes. The strong C-F bond of perfluorobenzene is cleaved under reducing conditions in the presence of a rare-earth metal iodide to form initially an equimolar mixture of a metal fluoride and a metal perfluorophenyl complex; the latter eventually undergoes β-F elimination to a metal fluoride. A similar reactivity is observed when reacting inverse sandwich rare-earth metal arene complexes with perfluorobenzene. All compounds were characterized by X-ray crystallography, multi-nuclear NMR spectroscopy, and elemental analysis.

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Fluorocarbons Modulate the Coordination Sphere of f‐Element Complexes

Cited by 7 publications

References 24 publications

Stereochemistry of Complexes with Double and Triple Metal–Ligand Bonds: A Continuous Shape Measures Analysis

Stereochemistry of Complexes with Double and Triple Metal–Ligand Bonds: A Continuous Shape Measures Analysis

C–F→Ln/An interactions in synthetic f-element chemistry

Aromatic C–F Bond Activation by Rare-Earth-Metal Complexes

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