NORMAND Adrien Voir la fiche profil en français Français (FR)

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  • NORMAND Adrien
  • Statut : Researcher (CR)
  • Team : OCS
  • Function : Researchers
  • Tags : Catalysis, Coordination chemistry, Organometallic chemistry, Synthetic chemistry
  • ORCID : 0000-0002-8047-9386
  • Address :

    ICMUB Institut de Chimie Moléculaire de l'Université de Bourgogne
    Bât. MIRANDE - Aille B - Bureau B210
    9 Avenue Alain Savary
    21000 Dijon – France

  • Tél : +33 380 396 880
  • adrien.normand@u-bourgogne.fr

2016: CNRS research associate, ICMUB.
2012-2016: Postdoc / Temporary lecturer, Université de Bourgogne (Pr P. Le Gendre) and WWU Münster (Pr G. Erker).
2009-2012: Research portfolio manager (« sustainable chemistry » programmes), Agence Nationale de la Recherche (Pr P. Cognet).
2008-2009: Postdoc, University of Ottawa (Pr D. Fogg).
2007-2008: Industrial postdoc, Sanofi-Aventis (P. Mailliet), Vitry-sur-Seine.
2007: PhD in chemistry, Cardiff University (Pr K. J. Cavell).

I am interested in the chemistry of transition metals and main group elements (included, but not limited to, titanium and phosphorus). Particular emphasis is placed on:

  • ü The synthesis and characterisation of organometallic compounds.
  • ü  The elucidation of questions pertaining to the nature of metal-ligand interactions: links between experiments and theory, epistemological implications (what is a chemical bond?).
  • ü  Reactivity studies, notably in small molecule activation (H2, CO2, P4).
  • ü  Applications to catalysis.

Current projects:

With P. Le Gendre (ICMUB) and G. Erker (WWU Münster), we are studying the properties of Cp2Ti+ or Cp2Zr+ cations stabilised by a phosphido (PR2-) or amido (NR2-) ligand. These complexes contain a Lewis acid and a Lewis base inside the same molecule, which enables them to activate organic substrates (H2, CO2…)in a cooperative manner (acid-base cooperativity).

normand adrien fig01

This work has shown that Ti-P bonds could be cleaved homolytically to generate a Ti(III) metalloradical and a phosphinyl radical (PR2). We now wish to harness this reactivity and prepare diradical catalysts which could act cooperatively (radical cooperativity). To this end, we are developing new ligand frameworks in order to stabilise these reactive species.

normand adrien fig02

Other ongoing projects include:

  • With P. Le Gendre (ICMUB), S. Dagorne (Unistra) and A. Auffrant (École polytechnique), the catalytic applications of “phosphasalen” complexes.
  • With M. Iglesias Alonso (Universidad de Zaragoza), the coordination chemistry of “N-heterocyclic olefin” complexes of Ti and Zr.

 

“Direct P-functionalization of azobenzene by a cationic phosphidozirconocene complexA. T. Normand*, C. G. Daniliuc, G. Kehr, P. Le Gendre and G. Erker, Dalton Trans., 2016, 3711-3714.

“Phosphido- and amidozirconocene cation-based frustrated Lewis pair chemistry” A. T. Normand, C. G. Daniliuc, B. Wibbeling, G. Kehr, P. Le Gendre* and G. Erker*, J. Am. Chem. Soc., 2015 , 137, 10796-10808 .

Titanium imido complexes stabilised by bis(iminophosphoranyl)methanide ligands: the influence of N-substituents on solution dynamics and reactivityA. T. Normand, A. Massard, P. Richard, C. Canovas, C. Balan, M. Picquet, A. Auffrant* and P. Le Gendre*, Dalton Trans., 2014, 15098-15110.

N-heterocyclic carbenes bearing two, one and no nitrogen atoms at the ylidene carbon: insight from theoretical calculationsA. A. Tukov, A. T. Normand* and M. S. Nechaev*, Dalton Trans., 2009, 7015-7028.

Mechanisms in the reaction of palladium(II)–π-allyl complexes with aryl halides: evidence for NHC exchange between two palladium complexes A. T. Normand, M. S. Nechaev* and K. J. Cavell*, Chem. Eur. J., 2009, 15, 7063-7073.

 

Communication

Teaching

I am a synthetic chemist, an organic “monkey” by training. Over the years, I have shifted my research towards coordination chemistry. My “core business” lies in the handling of species that are sensitive to laboratory conditions (oxygen, water, light, heat), including pyrophoric compounds: white phosphorus (P4), silane gas (SiH4), neat trimethylaluminium and the like.

I am one of a few chemists in Europe who has mastered the allotropic conversion of phosphorus as originally reported by Baker at the end of the XIXth century. For an adaptation of this procedure, see the supporting information of our paper (Chem. Sci. 2021, 12, 253).

DISCLAIMER: the procedure outlined below is for illustration purposes only, see the full text of the publication for the complete procedure together with hazards assessment.

 

image 1   image 2
 Step 1: beginning of thermolysis. The heatgun is placed underneath the pile of red phosphorus. Note that the Schlenk tube is placed under static vacuum and lubricated with Apiezon H grease.    Step 2: after a few minutes, white phosphorus condenses on the cooler parts of the Schlenk tube. The heatgun is progressively moved towards the bottom end of the tube (right).
     
 Step 3: after cooling and transfer in the glovebox, the Schlenk tube is scraped and the solids are extracted with CH2Cl2 in an ordinary Schlenk flask lubricated with Dow Corning Si grease.    Step 4: after overnight extraction, the solids are filtered over a grade 4 glass frit in the glovebox. Note that for this batch, residual lumps of P4 can be observed. A second extraction was necessary in order to completely separate P4 from red phosphorus.
     
Step 5: the CH2Cl2 solution is evaporated to dryness with a vacuum line.   Step 6: finely divided P4 is obtained after collection in the glovebox.
     
Step 7: residues of P4 are burned under a flow of air. Note that this step is performed with the sash of the fumehood completely lowered, in order to protect the operator from toxic PxOy fumes. A larger metal pan may also be used as a protection from airborne burning P4 particles if required. The glassware may then be cleaned with water and cleaning powder.   Step 8: the Schlenk tube can now be cleaned safely.
     

 

 

 

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