Institut de Chimie Moléculaire et des Matériaux d'Orsay

Academic background : Magistère de physico-chimie moléculaire (Licence, maîtrise, DEA, ENS Cachan, Université Paris-Sud, 1997-2001)

Agrégation de Sc. Physiques option Chimie (2001)

PhD : Synthesis of high spin anisotropic cyanide-bridged polynuclear complexes (Pr Talal Mallah, Université Paris Sud 2002-2005)

Post-doc : Synthesis of aminoacids-based  nanoporous chiral metal-organic frameworks (Pr. Matt Rosseinsky, University of Liverpool, 2005-2008)

CNRS researcher.

*2008-2016 : UMR8601, Université Paris Descartes, groupe du Pr Olivia Reinaud.

*2016-... : UMR 8182, ICMMO, Université Paris Saclay, groupe du Pr Frédéric Banse.

H₂O₂ and O₂ activation by non-heme complexes for mild substrate oxidation: catalysis and mechanistic studies

Non-heme iron enzymes are capable of carrying out substrate oxidation reactions under mild conditions (37°C, Patm), activating O₂ and releasing water as a by-product. To achieve these remarkable performances, difficult to attain with conventional catalysts, very fine control of the 1^st and 2^nd coordination spheres is required.

Our approach consists in synthesizing model non-heme iron complexes and modulating these two parameters within their structure in order to assess their impact on iron reactivity, and optimize their performance in O₂ or H₂O₂ activation, the aim being to generate Fe^IIIOOH, Fe^IV=O or other species known to be capable of oxidizing substrates.

Below are a few examples of 1^st and 2^nd coordination sphere modification strategies, which have a significant impact on the properties of iron complexes.

I/ 1^st coordination sphere effects

• Lability and impact on reactivity

"Hydroxylation of Aromatics by H₂O₂ Catalyzed by Mononuclear Non-heme Iron Complexes: Role of Triazole Hemilability in Substrate-Induced Bifurcation of the H₂O₂ Activation Mechanism", Chem. Eur. J., 2020, 26, 659-668. Jean-Noël Rebilly,* Wenli Zhang, Christian Herrero, Hachem Dridi, Katell Sénéchal-David, Régis Guillot and Frédéric Banse.*

mtL₄²Fe^II(OTf)₂ reacts with H₂O₂ to yield a (N₄)Fe^III(OOH)(MeCN) intermediate where triazole remains dangling. The hemilability of triazole then allows for a substrate-triggered switch of the Fe^III(OOH) activation pathway, yielding a reactive {(N₅)Fe^IV=O; OH^.} species instead (N₄)Fe^V=O(OH) obtained in the absence of substrate. This significantly impacts regioselectivity in aromatic hydroxylation.

• Redox potential and influence on the reductive O₂ activation mode

"A Tale of Two Complexes: Electro-Assisted Oxidation of Thioanisole by an “O2 Activator/Oxidizing Species” Tandem System of Non-Heme Iron Complexes", Chem. Eur. J., 2022, 28, e202200217. Amanda Lyn Robinson, Jean-Noël Rebilly,* Régis Guillot, Christian Herrero, Hélène Maisonneuve and Frédéric Banse.*

Increasing the electronic density at the Fe site lowers the Fe^III/II potential below a threshold where Fe^II is able to spontaneously react with O₂. Above this threshold, Fe^II does not react with O₂: electron input is required to achieve it.

II/ 2^nd coordination sphere effects

• Modification of the activation pathway of hydrogen peroxide by a 2^nd sphere proton donor

"Second-sphere effects on H₂O₂ activation by non-heme Fe^II complexes: role of a phenol group in the [H₂O₂]-dependent accumulation of Fe^IVO vs. Fe^IIIOOH", Chemical Science, 2021, 12, 15691-15699. Jean-Noël Rebilly,* Christian Herrero, Katell Sénéchal-David, Régis Guillot, Tanya Inceoglu, Hélène Maisonneuve and Frédéric Banse.* 

Redox metalloenzymes achieve very selective oxidation reactions under mild conditions using O₂ or H₂O₂ as oxidants and release harmless side-products like water. Their oxidation selectivity is intrinsically linked to the control of the oxidizing species generated during the catalytic cycle. To do so, a second coordination sphere is used in order to create a pull effect during the activation of O₂ or H₂O₂, thus ensuring a heterolytic O–O bond cleavage. Herein, we report the synthesis and study of a new non-heme Fe^II complex bearing a pentaazadentate first coordination sphere and a pendant phenol group. Its reaction with H₂O₂ generates the classical Fe^IIIOOH species at high H₂O₂ loading. But at low H₂O₂ concentrations, an Fe^IVO species is generated instead. The formation of the latter is directly related to the presence of the 2^nd sphere phenol group. Kinetic, variable temperature and labelling studies support the involvement of the attached phenol as a second coordination sphere moiety (weak acid) during H₂O₂ activation. Our results suggest a direct Fe^II → Fe^IVO conversion directed by the 2^nd sphere phenol via the protonation of the distal O atom of the Fe^II/H₂O₂ adduct leading to a heterolytic O–O bond cleavage.

• Optimization of the potential  for the reductive activation of  O₂ by a 2^nd sphère H bond donor

"Significant Effect of 2^nd Sphere Interactions on the Reductive Activation of O₂ by non-heme Iron(II) Complexes – Application to the Electroassisted Oxidation of Thioanisole", European Journal of Inorganic Chemistry, 2024, 27, e202300694. Amanda Lyn Robinson, Eva Bannerman, Régis Guillot, Christian Herrero, Katell Sénéchal-David, Eric Rivière, Frédéric Banse* and Jean-Noël Rebilly*

2^nd sphere hydrogen bonds within non-heme iron complexes significantly improves the potential of the reductive O₂ activation process, by generating stabilizing interactions within the Fe/O₂ adduct. O₂ can be activated at a much more favorable potential, which we took advantage of to achieve the electroassisted oxidation of thioanisole by O₂.

III/ Reductive O₂ activation and tandem catalysis: Association of an O₂-reductive-activator complex and a 2^nd complex activating superoxide to an oxidizing species

"A Tale of Two Complexes: Electro-Assisted Oxidation of Thioanisole by an “O₂ Activator/Oxidizing Species” Tandem System of Non-Heme Iron Complexes", Chem. Eur. J., 2022, 28, e202200217. Amanda Lyn Robinson, Jean-Noël Rebilly,* Régis Guillot, Christian Herrero, Hélène Maisonneuve and Frédéric Banse.*

The electro-assisted oxidation of thioanisole by O₂ was achieved using a tandem couple “O₂ activator/oxidation system” of non-heme complexes: at an electrode, L₂Fe^III(OTf) is reduced to Fe^II, which activates O₂ to superoxide and transfers it to (TPEN)Fe^II(PF₆)₂. The latter generates a reactive species capable of substrate oxygenation.

21/ Selective Fluorimetric Detection of Primary Alkylamines by a Calix[6]arene Funnel Complex, C. Rémy, H. Guyon, J.-N. Rebilly, I. Leray and O. Reinaud, Chem. Eur. J., 2017, 23, 8669-8677.

20/ Biomimetic cavity-based metal complexes, J.-N. Rebilly, B. Colasson, O. Bistri, D. Over and O. Reinaud, Chemical Society Reviews, 2015, 44, 467-489

19/ Calixarenes and resorcinarenes as scaffolds for supramolecular metallo-enzyme mimicry, J.-N. Rebilly and O. Reinaud, Supramolecular Chemistry, 2014, 26, 454-479

18/ A versatile strategy for appending a single functional group to a multifunctional host through host-guest covalent-capture, J.-N. Rebilly, A. Hessani, B. Colasson and O. Reinaud, Org. Biomol.Chem., 2014, 12, 7780 - 7785

17/ Iron Coordination Chemistry with New Ligands Containing Triazole and Pyridine Moieties. Comparison of the Coordination Ability of the N-Donors, N. Ségaud, J.-N. Rebilly, K. Sénéchal-David, R. Guillot, L. Billon, J.-P. Baltaze, J. Farjon, O. Reinaud and F. Banse, Inorg. Chem., 2013, 52, 691-700

16/ Guest-Triggered Zn(II) Trans location and Supramolecular Nuclearity Control in Calix[6]arene-Based Complexes, N. Bernier, N. Menard, B. Colasson, J.-N. Rebilly and O. Reinaud, Inorganic Chemistry, 2013, 52, 4683-4691.

15/ Supramolecular Bioinorganic Chemistry,J.-N. Rebilly and O. Reinaud*  in "Supramolecular Chemistry: From Molecules to Nanomaterials" Edited by Philip A. Gale (University of Southampton) et Jonathan W. Steed (Durham University), John Wiley & Sons, Ltd), 2012.

14/ Supramolecular control of hetero-multinuclear polytopic binding of metal ions (Zn^II, Cu^I) at a single calix[6]aren-based scaffold, J. N. Rebilly, O. Bistri, B. Colasson and O. Reinaud,Inorg. Chem., 2012, 51, 5965-5974.

13/ Supramolecular Copper Dioxygen Chemistry, J.-N. Rebilly and Olivia Reinaud,* in « Copper-Oxygen Chemistry » (chap 10. Edited by Kenneth D. Karlin and Shinobu Itoh, John Wiley & Sons, 2011.

12/ Synthesis and First Studies of the Host-Guest and Substrate Recognition Properties of a Porphyrin-Tethered Calix[6]arene Ditopic Ligand, C. Monnereau, J.-N. Rebilly and O. Reinaud, European Journal of Organic Chemistry, 2011, 166-175

11/ 1D Tubular and 2D Metal-Organic Frameworks Based on a Flexible Amino Acid Derived Organic Spacer, J.-N. Rebilly, J. Bacsa and M. J. Rosseinsky, Chem. Asian J. , 2009, 4, 892-903

10/ Chiral II-VI Semiconductor Nanostructure Superlattices Based on an Amino Acid Ligand, J.-N. Rebilly, P. W. Gardner, G. R. Darling, J. Bacsa and M. J. Rosseinsky, Inorg. Chem., 2008, 47, 9390-9399

9/ Large magnetic anisotropy in pentacoordinate Ni^II complexes, J.-N. Rebilly, G. Charron, E. Riviere, R. Guillot, A.-L. Barra, M. D. Serrano, J. van Slageren and T. Mallah, Chem. Eur. J., 2008, 14, 1169-1177

8/ Control of porosity geometry in amino acid derived nanoporous materials, J. Perez Barrio, J.-N. Rebilly, B. Carter, D. Bradshaw, J. Bacsa, A. Y. Ganin, H. Park, A. Trewin, R. Vaidhyanathan, A. I. Cooper, J. E. Warren and M. J. Rosseinsky, Chem. Eur. J., 2008, 14, 4521-32

7/ Glycoligands tuning the magnetic anisotropy of Ni^II complexes, G. Charron, F. Bellot, F. Cisnetti, G. Pelosi, J.-N. Rebilly, E. Riviere, A.-L. Barra, T. Mallah and C. Policar, Chem. Eur. J., 2007, 13, 2774-2782

6/ A family of nanoporous materials based on an amino acid backbone, R. Vaidhyanathan, D. Bradshaw, J.-N. Rebilly, J. P. Barrio, J. A. Gould, N. G. Berry and M. J. Rosseinsky, Angew. Chem. Int. Ed., 2006, 45, 6495-6499

5/ Synthesis of single Molecule Magnets using metallocyanates, J.-N. Rebilly and T. Mallah, Struct. Bond., 2006, 122, 103

4/ Magnetic anisotropy of two trinuclear and tetranuclear Cr(III)Ni(II) cyanide-bridged complexes with spin ground states S=4 and 5, J.-N. Rebilly, L. Catala, G. Charron, G. Rogez, E. Riviere, R. Guillot, P. Thuery, A.-L. Barra and T. Mallah, Dalton Trans., 2006, 2818-2828

3/ One step assembly of a nonanuclear (Cr^III₂Ni₇^II) bimetallic cyanide bridged complex, J. N. Rebilly, L. Catala, E. Riviere, R. G. Guillot, W. Wernsdorfer and T. Mallah, Chem. Commun., 2006, 735-737

2/ Very large ising-type magnetic anisotropy in a mononuclear Ni^II complex, G. Rogez, J. N. Rebilly, A. L. Barra, L. Sorace, G. Blondin, N. Kirchner, M. Duran, J. van Slageren, S. Parsons, L. Ricard, A. Marvilliers and T. Mallah, Angew. Chem., Int. Ed., 2005, 44, 1876-1879.

1/ A Tetranuclear Cr^IIINi^II₃ Cyano-Bridged Complex Based on M(tacn) Derivative Building Blocks, J.-N. Rebilly, L. Catala, E. Rivière, R. Guillot, W. Wernsdorfer and T. Mallah, Inorganic Chemistry, 2005, 44, 8194-8196.