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Design of New Molecular and Supramolecular Compounds of F Elements for the Activation of Co2 and Related Small Molecules

English title Design of New Molecular and Supramolecular Compounds of F Elements for the Activation of Co2 and Related Small Molecules
Applicant Mazzanti Marinella
Number 157158
Funding scheme Project funding (Div. I-III)
Research institution Institut des sciences et ingénierie chimiques EPFL - SB - ISIC
Institution of higher education EPF Lausanne - EPFL
Main discipline Inorganic Chemistry
Start/End 01.05.2015 - 30.04.2018
Approved amount 394'926.00
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Keywords (6)

Uranium; Redox-active ligands; Reactivity; Small Molecules Activation; Coordination chemistry; Lanthanides

Lay Summary (French)

Lead
Le dioxyde de carbone, très abondant, éveille aujourd’hui un intérêt tout particulier en tant que potentielle source de composés C1. Le fort caractère oxophile des éléments f, les rendent particulièrement intéressants pour la conception de nouveaux systèmes moléculaires capables de fixer et réduire le CO2. L’objectif global de ce projet est de développer des complexes moléculaires d’éléments f capables de promouvoir la transformation des petites molécules et du CO2 en particulier. Pour cela nous nous intéresserons à des ligands capables de conférer des propriétés spécifiques aux centres métalliques et nous acquerrons une profonde compréhension de cette chimie, des structures électroniques et de la réactivité de ces nouveaux complexes moléculaires et supramoléculaires d’éléments f. Ceci nous permettra d’optimiser les paramètres moléculaires contrôlant la réactivité de ces systèmes avec le CO2.
Lay summary

L’activation et la fonctionnalisation des petites molécules inertes comme CO, CO2, et N2, seraient un excellent moyen de résoudre quelques uns des plus importants problèmes énergétiques de la planète.

Le dioxyde de carbone, très abondant, éveille aujourd’hui un intérêt tout particulier en tant que potentielle source de composés C1. Cependant, une transformation sélective et peu coûteuse en énergie de cette molécule très stable reste l’un des plus grands défis de la chimie de synthèse actuelle. Les complexes métalliques capables d’activer le dioxyde de carbone par un mécanisme bien défini sont donc très attractifs d’un point de vue fondamental pour la compréhension de la réactivité du CO2 et pourraient être d’une grande importance économique dans le domaine des nouveaux combustibles.

Le fort caractère oxophile des éléments f, la flexibilité de leur sphère de coordination et la large gamme de rayons ioniques et de potentiels redox disponibles dans cette série d’ions les rendent particulièrement intéressants pour la conception de nouveaux systèmes moléculaires capables de fixer et réduire le CO2. L’objectif global de ce projet est de développer des complexes moléculaires d’éléments f capables de promouvoir la transformation des petites molécules et du CO2. Pour cela nous nous intéresserons à des ligands capables de conférer des propriétés spécifiques aux centres métalliques et nous acquerrons une profonde compréhension de cette chimie, des structures électroniques et de la réactivité de ces nouveaux complexes moléculaires et supramoléculaires d’éléments f. Ceci nous permettra d’optimiser les paramètres moléculaires contrôlant la réactivité de ces systèmes avec le CO2. Ce travail fournira des résultats sur l’activation du CO2 mais aussi, de façon plus générale, de nouvelles pistes pour la chimie réductrice des ions lanthanides et uranium et des accès à de nouvelles voies de synthèse d’intermédiaires originaux et très réactifs. 

 

Direct link to Lay Summary Last update: 31.03.2015

Responsible applicant and co-applicants

Employees

Publications

Publication
Reversible Dihydrogen Activation and Hydride Transfer by a Uranium Nitride Complex
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.
A versatile route to homo- and hetero-bimetallic 5f-5f and 3d-5f complexes supported by a redox active ligand framework
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.
Nitrogen reduction and functionalization by a multimetallic uranium nitride complex
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.
Ligand and Metal Based Multielectron Redox Chemistry of Cobalt Supported by Tetradentate Schiff Bases
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.
Metathesis of a U-V imido complex: a route to a terminal U-V sulfide
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.
CO Cleavage and CO 2 Functionalization under Mild Conditions by a Multimetallic CsU 2 Nitride Complex
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.
CO Cleavage and CO2 Functionalization under Mild Conditions by a Multimetallic CsU2 Nitride Complex
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, 209-212.
Facile CO Cleavage by a Multimetallic CsU2 Nitride Complex
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.
Nucleophilic Reactivity of a Nitride-Bridged Diuranium(IV) Complex: CO2 and CS2 Functionalization
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.
Synthesis and Structure of Nitride-Bridged Uranium(III) Complexes
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.
Synthesis and reactivity of a terminal uranium(IV) sulfide supported by siloxide ligands
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.
Uranium(IV) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium-sulfur bond
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.
CO2 conversion to isocyanate via multiple N-Si bond cleavage at a bulky uranium(III) complex
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, 15454-15457.
Lanthanide(II) Complexes Supported by N,O-Donor Tripodal Ligands: Synthesis, Structure, and Ligand-Dependent Redox Behavior
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.
Ferrocene-Based Tetradentate Schiff Bases as Supporting Ligands in Uranium Chemistry
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.

Collaboration

Group / person Country
Types of collaboration
Laurent Maron /Universite Toulouse France (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Dalton 2018 Talk given at a conference Small Molecule Activation by Multimetallic Uranium Complexes 03.04.2018 Warwick, Great Britain and Northern Ireland Mazzanti Marinella;
255h American Chemical Society Meeting Talk given at a conference Synthesis and Reactivity of Multimetallic Uranium Nitrides 18.03.2018 New Orleans, United States of America Mazzanti Marinella;
255h American Chemical Society Meeting Talk given at a conference Synthesis and Reactivity of Complexes of f Elements Supported by Siloxides 18.03.2018 New Orleans, United States of America Mazzanti Marinella;
Sillimans Lecture in Inorganic Chemistry Individual talk Small Molecule activation by multimetallic uranium complexes 20.12.2017 Yale, United States of America Mazzanti Marinella;
SCS fall meeting 2017 Talk given at a conference Small Molecule Activation at Multimetallic Uranium Nitrides 21.08.2017 Bern, Switzerland Falcone Marta;
Organometallics Gordon Research Conference Talk given at a conference Activation and Functionalization of Small Molecules by Multimetallic Uranium Complexes 09.07.2017 Newport, RI, United States of America Mazzanti Marinella;
28th Rare Earth Conference Talk given at a conference Small Molecule Activation by Multimetallic Uranium Nitrides 18.06.2017 Ames, Iowa, United States of America Mazzanti Marinella;
Inorganic Reaction Mechanisms Gordon Research Conference Poster Small Molecule Activation at Multimetallic Uranium Nitrides 05.03.2017 Galveston, Texas, United States of America Falcone Marta;
SCS fall meeting 2016 Poster Nucleophilic Reactivity of a Nitride-Bridged di-Uranium(IV) Complex: Small Molecules Activation 15.09.2016 Zurich, Switzerland Falcone Marta;
6th EuCheMS Chemistry Congress Sevilla Spain 2016 Talk given at a conference Small Molecule Activation by Complexes of Low-valent f Elements 11.09.2016 Sevilla , Spain Mazzanti Marinella;
6th EuCheMS Chemistry Congress Talk given at a conference Small Molecule Activation by Complexes of Low-valent f Elements 11.09.2016 Sevilla, Spain Mazzanti Marinella;
42nd International Conference in Coordination Chemistry Poster Nucleophilic Reactivity of a Nitride-Bridged di-Uranium(IV) Complex: Small Molecule Activation 03.07.2016 Brest, France Falcone Marta;
42nd International Conference in Coordination Chemistry Talk given at a conference Small Molecule Activation by Low-valent f Elements 03.07.2016 Brest, France Mazzanti Marinella;
Rubin Colloquium Individual talk New perspectives in uranium chemistry: from nuclear to single molecule magnets. 21.04.2016 Technion Institute, Israel Mazzanti Marinella;
Pacifichem 2015 Talk given at a conference Small Molecule Activation by Complexes of Low-Valent f Elements 15.12.2015 Honolulu, United States of America Mazzanti Marinella;
Pacifichem 2015 Talk given at a conference Ligand Versus Metal Centred Reactivity of Low Valent Uranium 15.12.2015 Honolulu, United States of America Mazzanti Marinella;
9th international conference on f-elements 2015 Talk given at a conference New Perspectives in Uranium Chemistry 06.09.2015 Oxford, Great Britain and Northern Ireland Mazzanti Marinella;
SCS fall meeting 2015 Poster URANIUM SCHIFF BASE COMPLEXES: ELECTRON STORAGE IN C-C BOND 04.09.2015 Lausanne, Switzerland Falcone Marta;


Communication with the public

Communication Title Media Place Year
New media (web, blogs, podcasts, news feeds etc.) A uranium complex offers new C-N bonds EPFL News International 2016

Awards

Title Year
SCS-DSM Award for best oral presentation in Inorganic and Coordination Chemistry 2017
SCS-DSM Award for best poster presentation in Inorganic and Coordination Chemistry 2016

Associated projects

Number Title Start Funding scheme
159180 Synthesis and Characterization of Thio-uranyl (US22+): Towards a Deeper Understanding of Actinide-Ligand Bonding 01.01.2015 International short research visits
178793 MULTIMETALLIC COMPLEXES OF F-ELEMENTS: ACTIVATION AND FUNCTIONALIZATION OF SMALL MOLECULES (N2, CO AND CO2) AND MAGNETIC PROPERTIES 01.09.2018 Project funding (Div. I-III)

Abstract

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.
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