Publication

Stabilization of the Oxidation State plus IV in Siloxide-Supported Terbium Compounds

Publications associées (33)

Stabilizing Unusual Oxidation States of Lanthanides in Molecular Complexes: Synthesis, Properties, and Reactivity

The chemistry of divalent lanthanides has generated increasing interest in the past years due to their redox properties and unique reaction pathways. Notably, molecular complexes of low-valent lanthanides have been shown to be suitable one-electron reducta ...

EPFL2022

Synthesis, structural characterization, and coordination chemistry of imidazole-based alkylidene ketenes

Rosario Scopelliti, Kay Severin, Farzaneh Fadaei Tirani, Paul Varava, Wolfram Feuerstein

Alkylidene ketenes typically display high intrinsic reactivity, impeding isolation on a preparative scale. Herein, we report the synthesis of alkylidene ketenes by reaction of imidazole-based diazoolefins with carbon monoxide. The good thermal stability of ...

2021

Picometer Resolution Structure of the Coordination Sphere in the Metal-Binding Site in a Metalloprotein by NMR

David Lyndon Emsley, Andrea Bertarello

Most of our understanding of chemistry derives from atomic-level structures obtained with single-crystal X-ray diffraction. Metal centers in X-ray structures of small organometallic or coordination complexes are often extremely well-defined, with errors in ...

2020

Accessing the plus IV Oxidation State in Molecular Complexes of Praseodymium

Marinella Mazzanti, Farzaneh Fadaei Tirani, Ivica Zivkovic

Out of the 14 lanthanide (Ln) ions, molecular complexes of Ln(IV) were known only for cerium and more recently terbium. Here we demonstrate that the +IV oxidation state is also accessible for the large praseodymium (Pr) cation. The oxidation of the tetraki ...

2020

Molecular Complex of Tb in the +4 Oxidation State

Rosario Scopelliti, Marinella Mazzanti, Ivica Zivkovic

Lanthanides (Ln) usually occur in the +3, or more recently the +2, oxidation states. The only example of an isolated molecular Ln(4+) so far remains Ce4+. Here we show that the +4 oxidation state is also accessible in a molecular compound of terbium as dem ...

2019

Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple-Decker Arene-Bridged Cerium(II) Sandwich

Rosario Scopelliti, Marinella Mazzanti, Rory Patrick Kelly

Organometallic multi-decker sandwich complexes containing f-elements remain rare, despite their attractive magnetic and electronic properties. The reduction of the Ce-III siloxide complex, [KCeL4] (1; L = OSi(OtBu)(3)), with excess potassium in a THF/tolue ...

2017

Biologically derived metal organic frameworks

Kyriakos Stylianou, Samantha Lynn Anderson

Metal organic frameworks (MOFs) are extended structures composed of a network of organic ligands and metal ions or clusters connected to each other via coordination bonds. The numerous choices of organic ligands and metal coordination geometries have led t ...

Elsevier2017

Water exchange studies of lanthanide complexes and aqua ions

Shima Karimi

Complexes of lanthanide (III) ions have been used in structural studies of biomolecules and as contrast agents (CA). Clinically approved CAs have only one water molecule in their first coordination sphere. Structure and water exchange rate of these complex ...

EPFL2016

Complexation of [Gd(DTTA–Me)(H2O)2]− by Fluoride and Its Consequences to Water Exchange

Lothar Helm, Loïck Moriggi, Shima Karimi, Gail Ruth Hunter

The displacement of water molecule(s) from the inner coordination sphere of [Gd(DTTA–Me)(H2O)2]− (DTTA = ethylenetriamine-N,N,N″,N″-tetraacetate) by fluoride has been studied by multinuclear NMR relaxation (1H, 17O, 19F) and DFT calculations. Fluoride anio ...

American Chemical Society2016

Lanthanide coordination chemistry: from old concepts to coordination polymers

Jean-Claude Bünzli

Because of their remarkable and unmatched optical and magnetic properties, the lanthanides are under the limelight when it comes to high technology. These elements are used in strategic applications such as optical glasses and lasers, telecommunications, l ...

Taylor & Francis2014

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