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Biography and Current Works
Research interests: Iminophosphoranes, mixed ligands, Coordination Chemistry, and Catalysis
Education:
2012: Habilitation Université Paris-Sud Orsay
1999-2002 : PhD University Pierre et Marie Curie (Paris VI)
“Tricarbonylmanganese Complexes : first functionnalizations by Pd-catalyzed reactions”
Supervisor: Dr. E. Rose.
1998-1999: Master of Science (DEA) in Organic and Bioorganic Chemistry in Paris VI
1997-1999: Magistère interuniversitaire de chimie at ENS Ulm (Paris VI, Paris VII, Paris XI)
Professional Experience :
Since 2005 CNRS researcher in « Laboratoire Hétéro-éléments et Coordination », Ecole Polytechnique, Palaiseau, CR1 since October 2009
2004-2005 : Post Doctoral position in « laboratoire de Chimie Organo-Minérale » (université L. Pasteur, Strasbourg) under the supervision of Dr. J.-P. Sauvage.
Theme “Synthesis, characterization and photochemical properties of Ir(III) complexes.”
2002-2004: Post Doctoral position in the “Laboratorium für Organische Chemie”. in ETH Zürich under the supervision of Pr. Dr. F. Diederich.
Theme “Synthesis and properties of polyethynylbutatrienes”
Award
CNRS Bronze Medal 2010
Supervision since 2006:
7 undergraduate students, 3 Postgraduate student, 8 PhD students (3 in co-supervision), and 8 post docs (6 in co-supervision).
Teaching responsibilities:
2006-2015: Examiner for the oral competitive exam for admission at the Ecole Polytechnique.
Since 2007: Examiner for the oral exam of international Master of Science in Molecular Chemistry
Since 2015: Teacher at the Master for Molecular Chemistry (Ecole polytechnique).
From 2017: Part time teacher at Ecole polytechnique (Bachelor programm and M2)
Scientific Production:
58 publications in peer-review international journals. 1 patent
19 invited conferences
42 oral communications
36 posters
Organisation of professional Meetings:
GECOM CONCOORD 2008, Dourdan
Journées de Chimie de Coordination, 2010, Palaiseau
Journée des terres rares, Palaiseau, 2015
Journée de Chimie ENS-X-ESPCI ParisTech, every year since 2010
Part-time Professor at the Chemistry Department (Ecole polytechnique) from 2017 teaching general chemistry for Bachelor programm and Transition metal catalyzed coupling reactions for the M2 Molecular Chemistry and Interfaces (MOCHI)
We are interested in synthesizing orginal ligand incorporating different heteroatoms, and in particular phosphorus. We study their coordination chemistry with the objective to develop catalysts. We most precisely focus on mixed ligands incorporating an electron-rich iminosphophorane moiety. For example we developed phosphorus analogue of the salen that we termed phosphasalen, which allow to develop efficient initiators for lactide ring opening polymerization when associated to Group 3 or 4 metals. We got also interested in the non-innocent character of phosphasalen upon oxidation, showing the existence of multiconfigurational ground state in Cu and Ni phosphasalen complexes. We also work on orginal cooperative ligands featuring a proton responsive moiety with the objective to deliver catalysts for ecocompatible reactions. Our coordination studies mainly focus on earth-abundant 1rst raw metals. Characterization of complexes involves multinuclear NMR (when applicable), IR and UV spectroscopies, cyclic voltammetry as well as X-ray diffraction.
keywords: coordination chemistry, iminophosphorane, mixed ligands.
Main Publications and Links
5 significant papers:
Ruthenium complexes featuring cooperative phosphine–pyridine–iminophosphorane (PNN) ligands: synthesis, reactivity and catalytic activity
T. Cheisson, L. Mazaud, A. Auffrant,* Dalton Trans., 2018, 47, 14521 - 14530.. text
-Phosphasalen vs salen ligands: what does the phosphorus change?
I. Mustieles-Marín, A. Auffrant,* Eur. J. Inorg. Chem., 2018, 1634-1644. cover,cover profile, text
-Electronic Structures of Mono-Oxidized Copper and Nickel Phosphasalen Complexes
I. Mustieles-Marín, T. Cheisson, R. Singh Chauhan, C. Herrero, M. Cordier, C. Clavaguéra,* G. Nocton,* A. Auffrant,*
Chem. Eur. J., 2017, 23, 17940-17953.text
-A Tetracoordinated Phosphasalen Nickel(III) Complex
T.-P.-A. Cao, G. Nocton, L. Ricard, X. F. Le Goff, A Auffrant,*
Angew. Chem. Int. Ed., 2014, 53, 5, 1368-1372.text
-Yttrium Phosphasalen Initiators for rac-Lactide Polymerization: Excellent Rates and High Iso-Selectivities
C. Bakewell, T.-P.-A. Cao, N. Long, X. F. Le Goff, A. Auffrant,* C. K. Williams,*
J. Am. Chem. Soc., 2012, 134, 51, 20577–20580.text
Pd(II) and Ni(II) complexes featuring a “phosphasalen” ligand: synthesis and DFT study.
T.-P.-A. Cao, S. Labouille, A. Auffrant,* Y. Jean,* X. F. Le Goff, P. Le Floch,
Dalton Trans. 2011, 40, 10029-10037.text
Exhaustive list of publications
57. Tridentate NNN Ligand Associating Amidoquinoline and Iminophosphorane: Synthesis and Coordination to Pd and Ni Centers
L. Mazaud, M. Tricoire, S. Bourcier, M. Cordier, V. Gandon,* A. Auffrant,* Organometallics, 2020, 39, 719-728.
56. Deciphering preferred geometries of pyridylmethylamines-based complexes: A robust strategy combining NMR, DFT and X-ray
Be. Large, M. Meddeb, J. E. H. Pucheta, A. Gaucher, M. Cordier, C. Gosmini, J. Farjon, * A. Auffrant, * D. Prim* Inorg. Chim. Acta, 2019, 498, 119070.
55. Ruthenium complexes featuring cooperative phosphine–pyridine–iminophosphorane (PNN) ligands: synthesis, reactivity and catalytic activity
T. Cheisson, L. Mazaud, A. Auffrant,* Dalton Trans., 2018, 47, 14521 - 14530.
54. Cobalt-Catalyzed Formation of Functionalized Diarylmethanes from Benzylmesylates and Aryl Halides
B. R. P. Reddy, S. Chowdury, A. Auffrant,* C. Gosmini* Adv. Synth. Catal., 2018, 360, 3026-3029.
53. Synthesis and Reactivity of Low-Valent f-Element Iodide Complexes with Neutral Iminophosphorane Ligands
T. Cheisson, L. Ricard, F. W ; Heinemann, K. Meyer,* A. Auffrant,* G. Nocton* Inorg. Chem., 2018, 57, 9230-9240.
52. Cobalt-Catalyzed Formation of 2-Pyridylzinc Reagents and Their Subsequent Coupling
S. Linke, S. M. Manolikakes, A. Auffrant,* C. Gosmini* Synthesis, 2018, 50, 2595-2600.
51. Phosphasalen vs salen ligands: what does the phosphorus change?
I. Mustieles-Marín, A. Auffrant,* Eur. J. Inorg. Chem., 2018, 1634-1643.
50. Electronic Structures of Mono-Oxidized Copper and Nickel Phosphasalen Complexes
I. Mustieles-Marín, T. Cheisson, R. Singh Chauhan, C. Herrero, M. Cordier, C. Clavaguéra,* G. Nocton,* A. Auffrant,* Chem. Eur. J., 2017, 23, 17940-17953.
49. Cobalt-catalyzed reductive cross-coupling between benzyl chlorides and aryl halides
S. Pal, S. Chowdhury, E. Rozwadowski, A. Auffrant,* and C Gosmini*, Adv. Synth. Catal. 2016, 358, 2431-2435.
48. Palladium(II) complexes featuring a mixed Phosphine-Pyridine-Iminophosphorane pincer ligand : synthesis and reactivity
T. Cheisson, and A. Auffrant*, Dalton Trans., 2016, 45, 2069 - 2078.
47. η5–η1 Switch in Divalent Phosphaytterbocene Complexes with Neutral Iminophosphoranyl Pincer Ligands: Solid-State Structures and Solution NMR 1JYb–P Coupling Constants
Thibault Cheisson, A. Auffrant,* G.Nocton,* Organometallics, 2015, 34, 5470–5478
46. Cobalt-Catalyzed Electrophilic Cyanation of Arylzinc Halides with N-cyano-N-phenyl-p-methyl-benzenesulfonamide (NCTS),
Y. Cai, X. Qian, A. Rérat, A. Auffrant, C. Gosmini* Adv. Synth. Catal., 2015, 357, 3419-3423.
45. Nickel complexes featuring iminophosphorane-phenoxide ligands for catalytic ethylene dimerization
T. Cheisson, T.-P.-A Cao, X. F. Le Goff, A. Auffrant*, Organometallics, 2014, 33, 6193-6199.
44. Versatile Coordination Chemistry of a Bis(methyliminophosphoranyl)pyridine Ligand on Copper Centres
T. Cheisson, A. Auffrant,* Dalton Trans., 2014, 43, 13399-13409
43. Titanium imido complexes stabilised by bis(iminophosphoranyl)methanide ligands: the influence of N-substituents on solution dynamics and reactivity
A. T. Normand, A. Massard, P. Richard, C. Canovas, C. Balan, M. Picquet, A. Auffrant,* P. Le Gendre,* Dalton Trans. 2014, 43, 149111-15246.
42. A Tetracoordinated Phosphasalen Nickel(III) Complex
T.-P.-A. Cao, G. Nocton, L. Ricard, X. F. Le Goff, A Auffrant,* Angew. Chem. Int. Ed., 2014, 53, 5, 1368-1372.
41. Ethylene dimerization catalyzed by mixed phosphine–iminophosphorane nickel(II) complexes: a DFT investigation
V. Tognetti, A. Buchard, A. Auffrant, I. Ciofini, P. Le Floch , C. Adamo,* J. Mol. Modeling, 2013, 19, 5, 2107-2118.
40. Cobalt-Catalyzed Electrophilic Amination of Arylzincs with N-Chloroamines
X. Qian, Z. Yu, A. Auffrant, C. Gosmini,* Chem. Eur. J., 2013, 19, 20, 6225-6229.
39. Yttrium Phosphasalen Initiators for rac-Lactide Polymerization
C. Bakewell, T.-P.-A. Cao, X. F. Le Goff, N. Long, A. Auffrant,* C. K. Williams,* Organometallics, 2013, 32, 5, 1475-1483.
38. Yttrium Phosphasalen Initiators for rac-Lactide Polymerization: Excellent Rates and High Iso-Selectivities
C. Bakewell, T.-P.-A. Cao, N. Long, X. F. Le Goff, A. Auffrant,* C. K. Williams,* J. Am. Chem. Soc., 2012, 134, 51, 20577–20580.
37. Synthesis and Characterization of Bidentate Rare-Earth Iminophosphorane o-Aryl Complexes and Their Behavior as Catalysts for the Polymerization of 1,3-Butadiene
E. Martinez-Arripe, F. Jean-Baptiste-Dit-Dominique, A. Auffrant, X. F. Le Goff, J. Thuilliez, F. Nief,* Organometallics, 2012, 31, 4854-4861.
36. Phosphasalen Yttrium Complexes: Highly Active and Stereoselective Initiators for Lactide Polymerization
T.-P.-A. Cao, A. Buchard, X. F. Le Goff, A. Auffrant,* C. K. Williams,* Inorg. Chem., 2012, 51, 40, 2157-2169.
35. Exemples de catalyseurs à ligands iminophosphoranes
A. Auffrant
L’Actualité Chimique, Janvier 2012, 359, 13-19.
34. Cobalt-catalyzed Reductive allylation of alkyl halides with allylic acetates or carbonates
X. Qian, A. Auffrant, A. Felouat, C. Gosmini,* Angew. Chem. Int. Ed., 2011, 50, 10402-10405.
33. Pd(II) and Ni(II) complexes featuring a “phosphasalen” ligand: synthesis and DFT study.
T.-P.-A. Cao, S. Labouille, A. Auffrant,* Y. Jean,* X. F. Le Goff, P. Le Floch, Dalton Trans. 2011, 40, 10029-10037.
32. Tridentate and Tetradentate Iminophosphorane-Based Ruthenium Complexes in Catalytic Transfer Hydrogenation of Ketones
H. Dyer, A. Picot, A. Auffrant, L. Vendier, P. Le Floch and S. Sabo-Etienne,* Organometallics, 2011, 30, 1478-1486.
31. Bis-Phosphorus(V) Stabilized Carbene Complexes
H. Heuclin, M. Fustier, A. Auffrant, N. Mézailles,* Lett. . Org. Chem., 2010, 7, 8, 596-611.
30. Facile synthesis of bifunctional ligands using LiCH2PPh2=NPh obtained from [PhNH-PPh3+] [Br-].
T.-P.-A. Cao, E. Payet, A. Auffrant,* X. F. Le Goff, P. Le Floch, Organometallics, 2010, 29, 3991-3996.
29. Iminophosphorane based [P2N2] rhodium complexes: synthesis, reactivity, and application in catalysed transfer hydrogenation of polar bonds.
A. Buchard, E. Payet, A. Auffrant,* X. F. Le Goff, P. Le Floch,* New J. Chem., 2010, 34, 2943-2949.
28. Iminophosphorane Neodymium(III) complexes as efficient initiators for lactide polymerisation
A. Buchard, R. H. Platel, A. Auffrant, X. F. Le Goff, C. K. Williams,* P. Le Floch,* Organometallics, 2010, 29, 2892-2900.
27. Phosphine- and thiophosphine-amine ligands: lithiation and coordination to Rh(I)
E. Payet, A. Auffrant,* X. F. Le Goff, P. Le Floch,* J. Organomet. Chem., 2010, 695, 1499-1506.
26. Interplay Between Hydrido/Dihydrogen and Amine/Amido Ligands in Ruthenium Catalyzed Transfer Hydrogenation of Ketones
A. Picot, H. Dyer, A. Buchard, A. Auffrant, L. Vendier, P. Le Floch and S. Sabo-Etienne,* Inorg. Chem., 2010, 49,1310–1312
25. First neodymium(III) alkyl-carbene complex based on bis(iminophosphoranyl) ligands
A. Buchard, A. Auffrant, L. Ricard, X. F. Le Goff, R. H. Platel, C. K. Williams, P. Le Floch,* Dalton Trans., 2009, 10219-10222.
24. Chromium (III)-bis(iminophosphoranyl)methanido complexes: synthesis, X-ray crystal structures and catalytic ethylene oligomerization
C. Klemps, A. Buchard, R. Houdard, A. Auffrant, N. Mézailles, X. F. Le Goff, Louis Ricard, L. Saussine, L. Magna, P. Le Floch,*
New J. Chem., 2009, 33, 1748 – 1752.
23. Coordination of tetradentate X2N2 (X = P, S, O) ligands to iron(II) metal center and catalytic applications in the transfer hydrogenation of ketones
A. Buchard, H. Heuclin, A. Auffrant, X. F. Le Goff and P. Le Floch*
Dalton Trans., 2009, 1659-1667.
22. Bonding Mode of a Bifunctional P,Si-H ligand in the Ruthenium Complex "Ru(PPh2CH2OSiMe2H)3"
V. Montiel-Palma, O. Piechaczyk, A. Picot, A. Auffrant, L. Vendier, P. Le Floch,* S. Sabo-Etienne*
Inorg. Chem., 2008, 47, 8601-8603.
21. A Mixed Phosphine−Iminophosphorane Tetradentate Ligand: Synthesis, Coordination to Group 10 Metal Centers, and Use as Catalyst in Suzuki−Miyaura Coupling
A. Buchard, B. Komly, A. Auffrant, X. F. Le Goff and P. Le Floch*
Organometallics, 2008, 27, 4380–4385.
20. Bis phosphorus stabilised carbene complexe
T. Cantat, N. Mézailles, A. Auffrant, P. Le Floch*
Dalton Trans., 2008,1957-1972
19. Bimetallic Iridium(III) Complexes consisting of Ir(ppy)2 units (ppy : 2-phenyl-pyridine) and two laterally-connected N^N chelates as bridge : synthesis, separation and photophysical properties
A. Auffrant, A. Barbieri, F. Barigelletti, J. Lacour,* P. Mobian, J.-P. Collin,* J.-P. Sauvage,* B. Ventura
Inorg. Chem, 2007, 46,6911-6919.
18. Highly efficient P-N nickel(II) complexes for the dimerisation of ethylene
A. Buchard, A. Auffrant, C. Klemps, L. Vu-Do, L. Boubekeur, X. F. Le Goff, P. Le Floch*
Chem. Commun., 2007, 1502-1504
17. A new and convenient approach towards bis (iminophosphoranyl)methane ligands and their dicationic, cationic, anionic and dianionic derivatives.
M Demange, L. Boubekeur, A. Auffrant, N. Mézailles, L. Ricard, X. Le Goff , P. Le Floch,*
New J. Chem., 2006, 30, 1745-1754.
16. Dinuclear Iridium(III) Complexes consisting of back-to-back terpy-(Ph)n-terpy bridging ligands (n= 0, 1 or 2) and terminal cyclometallating tridentate N-C-N ligands
A. Auffrant, A. Barbieri, F. Barigelletti,* J.-P. Collin,* L. Flamigni, C. Sabatini, J.-P. Sauvage,
Inorg. Chem., 2006, 45, 10990-10997.
15. Nitrogen-Assisted Ortho Lithiation: One-Pot Synthesis of New Classes of Bidentate and Tetradentate Mixed P~N Ligands
L. Boubekeur, L. Ricard, N. Mézailles, M. Demange, A. Auffrant, P. Le Floch*
Organometallics, 2006, 25, 3091-3094.
14. Synthesis of 1,4-diethynyl and 1,1,4,4-tetraethynylbutatrienes.
A. Auffrant, F. Diederich,* C. Boudon, J.-P. Gisselbrecht, M. Gross
Helv. Chim. Acta, 2004, 87 ,12, 3085-3105.
13.Cationic (h6-arene)manganese linked to neutral (h6-arene)tricarbonylchromium complexes.
S. Schouteeten, J.-P. Tranchier, F. Rose-Munch,* E. Rose,* A. Auffrant, G. R. Stephenson
Organometallics, 2004, 23, 18, 4308-4316.
12. Peralkynylated buta-1,2,3-trienes: exceptionally low rotational barriers of cumulenic C=C bonds in the range of those of peptide C–N bonds
A. Auffrant, B. Jaun,* P. D. Jarowski, K. N. Houk,* F. Diederich*
Chem. Eur. J., 2004, 10, 2906-2911.
11. Synthesis of tricarbonyl h6- and h5-[(3-thiophenyl)organochromium and –manganese complexes
D. Prim, J. Giner-Planas, A. Auffrant, F. Rose-Munch,* E. Rose, J. Vaissermann
J. Organomet. Chem., 2003, 688, 273-279.
10. Synthesis, characterisation of (arene)tricarbonylchromium complexes linked to cationic Fe and Ru derivatives and studies of first hyperpolarisabilities by Hyper-Rayleigh Scattering
M. H. Garcia,* S. Royer, M. P. Robalo,* A. R. Dias, J.-P. Tranchier, R. Chavignon, D. Prim, A. Auffrant, F. Rose-Munch, E. Rose,* J. Vaissermann, A. Perssons, I. Asselberghs
Eur. J. Inorg. Chem, 2003, 3895-3904.
9. Palladium-catalyzed chloride substitution of h5-(chlorocyclohexadienyl)Mn(CO)3 complexes: an access to novel h6-(arene)Mn(CO)3+ cations.
A. Auffrant, D. Prim, F. Rose-Munch,* E. Rose, S. Schouteeten, J. Vaissermann
Organometallics, 2003, 22, 1898-1913.
8. Selective access to electron donating group substituted (h5-cyclohexadienyl)Mn(CO)3 complexes by bimetallic manganese-palladium activation.
A. Auffrant, D. Prim, F. Rose-Munch,* E. Rose,* J. Vaissermann
Organometallics, 2002, 21, 3500-3502.
7. Preparation of new (h6-arene)Mn(CO)3+ complexes involving Pd-catalysed/exo-hydride abstraction sequence.
A. Auffrant, D. Prim, F. Rose-Munch, E. Rose*
C.R. Chimie, 2002, 5, 137-141.
6. First synthesis of cationic [(h6-arene)Mn(CO)3] complexes substituted by resonance withdrawing groups.
A. Auffrant, D. Prim, F. Rose-Munch, E. Rose,* J. Vaissermann
Organometallics, 2001, 20, 3214-3216.
5. (h5-halogenocyclohexadienyl)Mn(CO)3 complexes : halogen substitution by arene derivatives.
D. Prim, A. Auffrant, F. Rose-Munch, E. Rose,* J. Vaissermann
Organometallics, 2001, 20, 1901-1903.
4. Organochromium/organoiron dipoles comprising (h6-arene)chromium and (h5-cyclohexadienyl)iron(1+) complexes linked with conjugated spacers
J.-P. Tranchier, R. Chavignon, D. Prim, A. Auffrant, J. Giner-Planas, F. Rose-Munch, E. Rose,* G. R. Stephenson*
Tetrahedron. Lett., 42, 2001, 3311-3313.
3. Bimetallic p-conjugated complexes modulated by a carbonyl spacer : synthesis of arene tricarbonylchromium-ferrocene derivatives.
D. Prim, A. Auffrant, Z. F. Plyta, J.-P Tranchier, F. Rose-Munch,* E. Rose
J. Organomet. Chem., 2001, 624, 124-130.
2. Synthesis of nitrile ligands bearing tricarbonyl(h6-arene)chromium complexes and conjugated spacers
J.-P. Tranchier, R. Chavignon, D. Prim, A. Auffrant, Z. F. Plyta, F. Rose-Munch, E. Rose*
Tetrahedron. Lett., 41, 2000, 2607-2610.
1. A new addition of aryl substituents to cyclohexadienyliron electrophiles in the development of routes to C12 building blocks for alkaloid synthesis.
Malkov, A. Auffrant, C. Renard, E. Rose, F. Rose-Munch, D. A. Owen, E. J. Sandoe, G. R. Stephenson*
Inorg. Chim. Acta, 296, 1999, 139-149.
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