Uranium; Redox-active ligands; Reactivity; Small Molecules Activation; Coordination chemistry; Lanthanides
Marta Falcone Lok Nga Poon Farzaneh Fadaei Tirani Marinella Mazzanti (2018), Reversible Dihydrogen Activation and Hydride Transfer by a Uranium Nitride Complex, in Angewandte Chemistry International Journal
, 57, 3697.
Camp C. Toniolo D. Andrez J. Pecaut J. Mazzanti M. (2017), A versatile route to homo- and hetero-bimetallic 5f-5f and 3d-5f complexes supported by a redox active ligand framework, in Dalton Transactions
, 46, 11145.
Falcone M. Chatelain L. Scopelliti R. Zivkovic I. Mazzanti M. (2017), Nitrogen reduction and functionalization by a multimetallic uranium nitride complex, in Nature
, 547, 332.
Andrez J. Guidal V. Scopelliti R. Pecaut J. Gambarelli S. Mazzanti M. (2017), Ligand and Metal Based Multielectron Redox Chemistry of Cobalt Supported by Tetradentate Schiff Bases, in Journal of the American Chemical Society
, 139, 8628.
Kelly R. P. Falcone M. Lamsfus C. A. Scopelliti R. Maron L. Meyer K. Mazzanti M. (2017), Metathesis of a U-V imido complex: a route to a terminal U-V sulfide, in Chemical Science
, 8, 5319.
Falcone Marta, Chatelain Lucile, Scopelliti Rosario, Mazzanti Marinella (2017), CO Cleavage and CO 2 Functionalization under Mild Conditions by a Multimetallic CsU 2 Nitride Complex, in CHIMIA International Journal for Chemistry
, 71(4), 209-212.
Falcone Marta, Chatelain Lucile, Scopelliti Rosario, Mazzanti Marinella (2017), CO Cleavage and CO2 Functionalization under Mild Conditions by a Multimetallic CsU2 Nitride Complex, in Chimia
Falcone M., Kefalidis C. E., Scopelliti R., Maron L., Mazzanti M. (2016), Facile CO Cleavage by a Multimetallic CsU2 Nitride Complex, in Angewandte Chemie International Edition
, 55, 12290-12294.
Falcone Marta, Chatelain Lucile, Mazzanti Marinella (2016), Nucleophilic Reactivity of a Nitride-Bridged Diuranium(IV) Complex: CO2 and CS2 Functionalization, in Angewandte Chemie International Edition
, 55, 4074-4078.
Chatelain Lucile, Scopelliti Rosario, Mazzanti Marinella (2016), Synthesis and Structure of Nitride-Bridged Uranium(III) Complexes, in Journal of the American Chemical Society
, 138, 1784-1787.
Andrez J., Pecaut J., Scopelliti R., Kefalidis C. E., Maron L., Rosenzweig M. W., Meyere K., Mazzanti M. (2016), Synthesis and reactivity of a terminal uranium(IV) sulfide supported by siloxide ligands, in Chemical Science
, 7, 5846-5856.
Rosenzweig M. W., Scheurer A., Lamsfus C. A., Heinemann F. W., Maron L., Andrez J., Mazzanti M., Meyer K. (2016), Uranium(IV) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium-sulfur bond, in Chemical Science
, 7, 5857-5866.
Camp Clement, Chatelain Lucile, Kefalidis Christos E., Pecaut Jacques, Maron Laurent, Mazzanti Marinella (2015), CO2 conversion to isocyanate via multiple N-Si bond cleavage at a bulky uranium(III) complex, in Chemical Communications
Andrez J., Bozoklu G., Nocton G., Pecaut J., Scopelliti R., Dubois L., Mazzanti M. (2015), Lanthanide(II) Complexes Supported by N,O-Donor Tripodal Ligands: Synthesis, Structure, and Ligand-Dependent Redox Behavior, in Chemistry- A European Journal
, 21(43), 15188-15200.
Camp Clement, Chatelain Lucile, Mougel Victor, Pécaut Jacques, Mazzanti Marinella (2015), Ferrocene-Based Tetradentate Schiff Bases as Supporting Ligands in Uranium Chemistry, in Inorganic Chemistry
, 54, 5774-5783.
Activation and functionalization of inert small molecules such as CO, CO2, and N2, would be an obvious way to solve some of the world’s most important energy problems. In particular carbon dioxide is currently receiving increasing attention as a potential abundant, low cost renewable C1 feedstock. However, selective, energy efficient transformation of the very stable CO2 molecule remains one of the biggest challenges in synthetic chemistry today. None of the metal-based catalysts identified so far for the chemical or electrochemical reduction of CO2 have the efficiency and stability required for the development of a commercially viable process. In particular, the mechanisms that lead to carbon dioxide reduction often remain unidentified, rendering the optimization of systems difficult. Metal complexes that activate CO2 in a well-defined manner are therefore highly desirable, and an understanding of fundamental CO2 reactivity would be of great importance for a post-fossil fuel economy. As a result, fundamental research in this field is rapidly increasing worldwide. The high oxophilicity of f elements, and the flexibility of their coordination sphere, together with the wide range of sizes and redox potentials found among these ions render them attractive for the design of new molecular systems for CO2 fixation and reduction. Moreover, the greater covalent contribution to bonding found in low-valent uranium complexes as compared to lanthanides, associated to the large size and coordination number of uranium, can promote original reactivity that is impossible with d-block transition metals. The global objective of this project is to develop molecular complexes of f elements capable of promoting the transformation of small molecules, and CO2 in particular, with the long-term goal of developing new homogeneous catalysts for the chemical and electrochemical transformation of carbon dioxide. We will do this by investigating ancillary ligands that confer specific properties to the metal centers and by gaining a deep understanding of the chemistry, electronic structure and reactivity of original molecular and supramolecular complexes of f elements. This will allow us to optimize the molecular parameters controlling the reactivity of these systems with CO2. Not only will this work lead to results for CO2 activation, but more generally it will provide new avenues for the reductive chemistry of lanthanide ions and uranium, and synthetic access to new types of highly reactive intermediates. The project will involve the development of: new rational strategies to prepare highly reactive complexes of f elements ; a comparative study of uranium and lanthanide ions associated to these ligands; the identification of original synthetic routes for the preparation of new mononuclear and polynuclear lanthanide and uranium architectures capable of storing a high number of electrons; the design of new molecular systems capable of activating carbon dioxide and other small molecules; the characterization of new f element complexes with unusual ligand or metal centered reactivity; and the implementation of the developed systems in closed synthetic cycles.