ionic liquids (il), use and specific task as solvent in catalytic reaction
DESCRIPTION
Ionic liquids (IL), use and specific task as solvent in catalytic reaction. Thibaut Gutel Ingénieur ESCOM. Laboratoire C2P2 Equipe. Directeurs de thèse : Catherine SANTINI et Yves CHAUVIN. 12-10-2007. Directeur Jean-Marie Basset. Contents : IL, solvent for catalytic reactions. - PowerPoint PPT PresentationTRANSCRIPT
Thibaut GutelIngénieur ESCOM
Ionic liquids (IL),use and specific task as
solvent in catalytic reaction
Directeur Jean-Marie Basset
Directeurs de thèse : Catherine SANTINI et Yves CHAUVIN
12-10-2007
Laboratoire C2P2
Equipe
2
Contents : IL, solvent for catalytic reactions
INTRODUCTION
RESULTS
A) Synthesis of IL
B) Behaviour of ionic compounds in IL
C) Behaviour of unsaturated substrates in IL
D) Generation of metal nanoparticles in IL
CONCLUSION
OUTLOOK
3
What are ionic liquids (IL) ?
IL are molten salts but Tmp < 100°C
Molten salts
Ionic liquids
Wasserschied et al. Ionic liquid in synthesis, 2003, Wiley-VCH
N P
N
N N
N
N
N
N
R1
R2
R1
R2
R4 R4
R3 R3
R1 R2
R1 R3 R1 R3
R1R2R2
ammoniun phosphonium pyrrolidinium
imidazolium triazolium pyridinium
Organic Cations
C+ Inorganic anions Organic anions
F-, Cl-, Br-, I- CH3CO2-, CH3SO4
-, C6H5SO3-
BF4-, PF6
-, SbF6-, AsF6
- CF3CO2-, C(CF3SO2)3
-
NO3-, ClO4
- CF3SO3- (=OTf)
AlxCl(3x+1), AlxEtxCl(2x+1) N(SO2CF3)2- (=NTf2)
CuCl2, AuCl4, ZnCl3-, SnCl3
- BR4-, R3BOH
Organic/Inorganic Anions
A-
106 possible associations of C+ / A-
4
Use of IL as solvent in industry
1995 : DifasolTM (IFP-Axens)
1995 : Synthesis of 2,5-dihydrofurane (Eastman Chem Co)
2003 : BASILTM (BASF) synthesis of phosphite
P
Cl
Cl
+ 2 EtOH
N NMe
P
OEt
OEt
+ N NMeH
Cl
[Ni]BMIMAlCl4
C8=
C4=
Favre et al. Petrol. Tech. 2002, 441, 104-109.
Maase et al. In PCT Int. Appl.; Basf: Germany, 2003; Vol. 2003062171, p 60
O O(C8H17)3(C18H37)P+I-
[Sn(C8H17)3]IFalling et al. In U.S. Pat.; Eastman Kodak Co., USA, 1993; p 8.
5
Why are IL interesting in catalysis ?
Low vapor pressure and non-flammable
Safety and ecological considerations
Low melting point and high thermal stability
Process optimization
Non-miscible with alkanes and/or water
Multiphase catalysis and immobilization of the catalyst
Tunable physico-chemical properties
Adjustment of viscosity, density or acidity
Welton et al. Ionic liquid in catalysis, Coord. Chem. Rev, 2004, 248, 2459-2477
Olivier-Bourbigou et al. Multiphase Homogeneous Catalysis, 2005, Wiley-VCH, 413-431
new opportunity as solvent for catalytic reaction
6
IL used as reaction media
Solvent IL solubilize reactants without modification
But IL are difficult to purify…
Presence of halide decrease activity in Michael addition
Handy et al. Tetrahedron Lett., 2003, 44, 8395-8397
increase activity in Heck reaction
Gallo et al. Dalton Trans., 2002, 4339–4342
Presence of water decomposition of water sensitive complex
increase activity of ruthenium catalyst
Daguenet et al. Organomet., 2004, 23, 6080-6083
7
Solvent IL solubilize reactants without modification
Ligand IL act as a ligand for the catalyst
Reactivity of C2-H : In situ formation of N-heterocyclic carbene
Presence of functional group : Coordination on PdNP
PdCl2
NN CNCl-
Pd NP
N
N
NC
Cl-
NN
CN
Cl-
Fei et al. Organomet. 2007, 26, 1588-1598
N
N
R
R
+ MLn
N
N
R
R
MLn-x
x
HMagna et al. Organomet., 2003, 22, 4418-4425
Hahn et al. Angew. Chem. Int. Ed., 2006, 45, 1348-1352
IL used as reaction media
8
Solvent IL solubilize reactants without modification
Ligand IL act as a ligand for the catalyst
Catalyst IL intervene as (co-)catalyst
Organocatalyst : Diels-Alder cycloaddition
Lewis acid : catalyst in Friedel-Crafts acylation
RCOCl + Al2Cl7- RCO+ + 2AlCl4
-
Stark et al. Dalton trans, 1999, 1, 63-66
R
X
O
BMIMAl2Cl7
R
O
Welton et al. Coord. Chem. Rev. 2004, 248, 2459-2477 N
N
R
R
O
O H
IL used as reaction media
9
Goal : Study of IL as solvents for catalytic reactions
Ionic liquids
Substrate Catalytic system
IL are non-innocent solvents
But IL are associations of C+/A- organized in 3D structure
10
IL, an association of C+/A- organized in 3D structure
Ionic exchange ?
C1+A1
- + C2+A2
- C1+A2
- +
C2+A1
-
Ionic
catalyst
IL
C+A- 3D organisation
Trapping ?
-cation Interaction ?
+
Unsaturated
substrates
Segregation in microdomains
Supramolecular matrix ?
11
Contents : IL, solvents for catalytic reactions
A) Synthesis of IL1. Choice of IL
2. Synthesis of IL
B) Behaviour of ionic compounds in IL
1. Study of ionic exchange in 23Na NMR
2. Influence of the catalytic activity
C) Behaviour of unsaturated substrates in IL
1. Study of aromatics/IL system by NMR
2. Study of aromatics/IL system by molecular dynamics
D) Generation of metal nanoparticles in IL
1. Influence of temperature
2. Influence of stirring
3. Influence of alkyl chain length at 0°C
12
A) IL used in this work
NNR1
R2
Me
H H
N
SO2
SO2 CF3
CF3
IL R1 R2
EMIMNTf2 C2H5 H
BMIMNTf2 C4H9 H
HMIMNTf2 C6H13 H
OMIMNTf2 C8H17 HDMIMNTf2 C10H21 H
BMMIMNTf2 C4H9 CH3
Why ?
Hydrophobic and liquid at room temperature
Planar cation
Non-coordinating anion
Easy to synthesize and to purify
C+ Alkylmethylimidazolium (R1R2MIM)
A- Bis(trifluoromethylsulfonyl)imide (NTf2)
13
1) Quaternisation of imidazole by halides
R1, R2 et R3 = alkyl
X= Cl or Br
2) Anion metathesis
R1, R2 et R3 = alkyl
X= Cl, Br, I
MY=LiNTf2, NaOTf, NaPF6, NaBF4
Good yield (75-80%)
Very high purity (halide < 50ppm and water < 50ppm)
A) Synthesis of imidazolium based IL
NNR1 R3NNR1 R3-X
X
R2 R2
Reflux
NNR1 R3 MY
X
R2
NNR1 R3
Y
R2
-MX
Magna, L. Thèse LCOMS, 2002
14
Contents : IL, solvents for catalytic reactions
A) Synthesis of IL
1. Choice of IL
2. Synthesis of IL
B) Behaviour of ionic compounds in IL1. Study of ionic exchange in 23Na NMR
2. Influence of the catalytic activity
C) Behaviour of unsaturated substrates in IL
1. Study of aromatics/IL system by NMR
2. Study of aromatics/IL system by molecular dynamics
D) Generation of metal nanoparticles in IL
1. Influence of temperature
2. Influence of stirring
3. Influence of alkyl chain length at 0°C
Ionic exchange ?
Ionic
catalyst
IL
C+A-
15
B) Dissolution of catalytic system in IL
Catalytic activity depends on the nature of IL with TPPMSNa
Catalyst dissolves in IL
3 BMIMBF4 + K3Co(CN)5 (BMIM)3Co(CN)5 + 3 KBF4
Suarez et al. Inorg. Chim. Acta, 1997, 207-209
Parshall et al. J. Am. Chem. Soc., 1972, 94, 8716-8719
PtCl2 Pt(SnCl3)53- + HPt(SnCl3)4
3-
Et4NSnCl3
CNCN
3PN
Ni(COD)2 / TPPMS-Na+
BMMIM+A-
373K / 3h
2M3BN
Vallée et al. J. Mol. Cat. A, 2004, 214, 71-81
IL Conversion in 3PN (%)
BMMIM+Cl
- 0
BMMIM+ZnCl3
- 17
BMMIM+Zn3Cl7
- 47
BMIM+OTf
- 27
BMMIM+BF4
- 27
BMIM+BF4
- 22
BMMIM+NTf2
- 96
BMIM+NTf2
- 88
BMMIM+PF6
- 93
16
B) Solvation of sodium salt in IL
Question : Na+A1- + C+A2
- ???
A1- : TPPMS-, AcO-
C+ : EMIM+, BMIM+, BMMIM+, Et4N+, Et4P+
A2- : Cl-, Br-, OTf-, BF4
-, PF6-, NTf2
-
Techniques : Study in 23Na NMR at solid state
Parameters : 1) Influence of temperature
2) Presence of water
17
B) Exchange reaction monitored by 23Na NMR
(ppm)-80-60-40-200204060
(ppm)-80-60-40-200204060
(ppm)-80-60-40-200204060
TPPMS-Na+
+ BMMIM+PF6-
120°C
(ppm)-80-60-40-200204060
Na+Cl- (ref)
Na+PF6 -
TPPMS-Na+
TPPMS-Na+
+ BMMIM+PF6-
100°C
TPPMS-Na+ + BMMIM+PF6- TPPMS-BMMIM+ +
Na+PF6-
IL
TPPMS-Na+
P
SO3 Na
TPPMS-Na+
=0ppm
= -27ppm
= -17ppm
18
B) Conclusion on ionic exchange
1) Exchange reaction is governed by the nature of anion
A2- = Cl- ; Br- ; OTf- total exchange C+/Na+
A2- = PF6- ; BF4
- partial exchange C+/Na+
A2- = NTf2
- no exchange C+/Na+
The exchange reaction can be predicted by the Hard and Soft Acid Base theory
2) In the case of partial exchange, this reaction is temperature dependent
higher temperature increases the rate of exchange
3) This ionic exchange is water independent
addition of water doesn’t increase the ratio of exchange
Na+A1- + C+A2
- C+A1- + Na+A-
19
Catalytic activity depends on the nature of IL
A- = Cl- ; Br- ; OTf- total exchange BMMIM+/Na+ low conversion
A- = PF6- ; BF4
- partial exchange BMMIM+/Na+ no recycling
A- = NTf2- no exchange BMMIM+/Na+ high conversion
Mobility of phosphine ligand is reduced after exchange
NiL4 NiL3 + L with L : TPPMS-BMMIM+ << TPPMS-Na+
DOSY measurements : D=6.91x10-12m2.s-1 D=10x10-
12m2.s-1
B) Explanation of the catalytic activity
CNCN
3PN
Ni(COD)2 / TPPMS-Na+
BMMIM+A-
373K / 3h
2M3BN
Vallée et al. J. Mol. Cat. A, 2004, 214, 71-81
NiL4
NiL3
L
CN
NiL2
CN
NiL2
NiL2
NC
L
3PN2M3BN
L
20
A) Synthesis of IL
1. Choice of IL
2. Synthesis of IL
B) Behaviour of ionic compounds in IL
1. Study of ionic exchange in 23Na NMR
2. Influence of the catalytic activity
C) Behaviour of unsaturated substrates in IL1. Study of aromatics/IL system by NMR
2. Study of aromatics/IL system by molecular dynamics
D) Generation of metal nanoparticles in IL
1. Influence of temperature
2. Influence of stirring
3. Influence of alkyl chain length at 0°C
Contents : IL, solvents for catalytic reactions
-cation Interaction
IL C+A-
3D Organized
21
A rigid network of H-bonded anions and cations
Holbrey et al. Dalton Trans., 2004, 226-2271
3D-Organization still presents at liquid state
Billard et al. Inorg. Chem. 2003, 42, 1726-1733
Dibrov et al. Acta Cryst., 2006, C62, o19±o21
C) IL, a highy organized network of C+ / A-
6,11Å
15,6Å
NNMe
H
Me
H H
NTf2
NNEt
Et
Et
H H
NTf2
22
Molecular dynamics of MMIMPF6
Formation of liquid clathrates of Benzene/MMIMPF6
C) Behaviour of aromatics in IL
Holbrey et al. Chem. Com., 2003, 476-477
Hadracre et al. J. Chem. Phys., 2003, 118,273-278
Deetlefs et al.. J. Phys. Chem. 2005, 109, 1593-1598
Harper et al. Mol. Phys. 2004, 102, 85-94
5.0ILArR
5.0ILArR
23
-cation interaction plays a crucial role in biochemistry
Binding energy of 10 to 30 kcal.mol-1
-cation interaction in chemistry
C) -cation interaction in chemistry
+
Ma et al. Chem. Rev., 1997, 97, 1303-1324Hunter et al. PNAS, 2002, 99, 4873-4876
Yamada et al. Tetrahedron Lett., 2004, 45, 7475-7478Yamada et al. J. Am. Chem. Soc, 2004, 126, 9862-9872
24
Question : Behaviour of unsaturated substrates in IL
Toluene IL : BMIMNTf2 and BMMIMNTf2
Techniques : 1) 1H NMR, ROESY and DOSY
2) Molecular dynamics
in collaboration with Dr Padua
Parameter : Influence of molar ratio (R) of toluene
R= moles of toluene for one mole of IL
C) Solvation of unsaturated substrates/IL system
25
C) Evolution of 1H chemical shifts
NNCH3
H
H2C
CH2
H2C
CH33
2
4 5
6
7
8
9
H H
CH3
H
H
H
H
H
HMe
Har
Har
Har
Har
Har
CD2Cl2
IL+ R To
BMIMNTf2
R=0.1
R=0.5
R=1
R=2
R=3
[ppm][ppm]10 8 6 4 2
BMIMNTf2
R=0.1
R=0.5
R=1
R=2
R=3
[ppm][ppm]10 8 6 4 2
96 7 8
96 7 8
9
2
7 8
9
7 8
96 7 8
4,5
4,5
4,5
4,5
4,5
6
6
3
3
3
3
3
2
2
2
2
Har
Har
Har
Har
Har
3 97 8
HMe
HMe
HMe
HMe
HMe
26
C) Evolution of 1H chemical shifts
BMMIMNTf
BMMIMNTf
R=0.1
R=0.5
R=1
R=2
R=3
[ ppm ] [ ppm ] 10 8 6 4 2
2
R=0.1
R=0.5
R=1
R=2
R=3
[ ppm ] [ ppm ] 10 8 6 4 2 [ ppm ] [ ppm ] 10 8 6 4 2
9 6 7 8
9 6 7 8
9
2
7 8
9 7 8
9 6 7 8 4,5
4,5
4,5
4,5
4,5
6
6
3
3
3
3
3
2
2
2
2 Har
Har
Har
Har
Har
3 9 7 8
HMe
HMe
HMe
HMe
HMe
4,5 6 2
NNCH3
CH3
H2C
CH2
H2C
CH33
2
4 5
6
7
8
9
H H
CH3
H
H
H
H
H
HMe
Har
Har
Har
Har
Har
27
C) Study of To/BMMIMNTf2 by ROESY NMR
Selective irradiation
C H 3
N N M e
M e
H H
Selective irradiation
C H 3
N N M e
M e
H H
ITo-IL measured rTo-IL ?
Ämmälahti et al. Magn. Reson, 1996,122, 230-232
Study of intermolecular interaction
61)(
ILTo
refrefILTo
IIrr
CH3
CH2
CH2CH2
CH3HIm
HAr
MeTo
28
Relative integrals in ROESY 1D
0,00
0,01
0,02
0,03
0,04
0,1 0,5 1 2 3
molar ratio R
Rel
ativ
e in
tegr
als
N NH3C
N NH3C
CH3
H
H2C
H2C
H(3)
H(3)
H(6)
H(6)
C) ROESY experiments
Evaluation of intermolecular distances
Chipot et al. J. Am. Chem. Soc., 1996, 118, 2998-3005
Deetlefs et al. J. Phys. Chem. B, 2005, 109, 1593-1598
61)(
ILTo
refrefILTo
IIrr
Estimation of minimum and maximum distances between H(Me) of toluene and H(3) & H(6) of
BMMIM
0,00
1,00
2,00
3,00
4,00
5,00
6,00
0,10 0,50 1,00 2,00 3,00
molar ratio (R)
dis
tan
ce (
A)
H(3) min
H(6) min
H(3) max
H(6) max
3.5Å
Benzene/DMIMPF6
N N M e B u
M e
H H
Selective irradiation
N N M e B u
M e
H H
2,3 < rref < 3,6Å Iref known
Selective irradiation
29
C) Molecular dynamics and radial distribution
Estimation of intermolecular distances (Pr Padua)
NNCH3
H
H2C
CH2
H2C
CH3
H HH3C
H H
H
HH
N
NH3C
CH3
CH2
H2CCH2
H3C
H
H
CH3
HH
H
H H1ILArR
30
C) To/BMIMNTf2 vs To/BMMIMNTf2
Evolution of 1H NMR at R = 0.1 to 1
To/BMIMNTf2 No evolution
To/BMMIMNTf2 Linear shift
ROESY experiments
To/BMIMNTf2 No interaction detected
To/BMMIMNTf2 Strong interaction at R=0.5 and 1
DOSY results
To/BMIMNTf2 Fast diffusion of toluene
To/BMMIMNTf2 Slow diffusion of toluene
Molecular dynamics
To/BMIMNTf2 Toluene close to alkyl chain
To/BMMIMNTf2 Toluene close to imidazolium ring
31
C) Conclusion on interaction To/IL
+
32
Contents : IL, solvent for catalytic reactions
A) Synthesis of IL
1. Choice of IL
2. Synthesis of IL
B) Behaviour of ionic compounds in IL
1. Study of ionic exchange in 23Na NMR
2. Influence of the catalytic activity
C) Behaviour of unsaturated substrates in IL
1. Study of aromatics/IL system by NMR
2. Study of aromatics/IL system by molecular dynamics
D) Generation of metal nanoparticles in IL1. Influence of temperature
2. Influence of stirring
3. Influence of alkyl chain length at 0°C
IL
3D organisation
Segregation in microdomains
Supramolecular matrix ?
33
Nanoclusters present unique properties between the bulk and the molecular species
Successful control of the size of MNP using rigid materials such as polymers or dendrimers
Astruc et al. Angew. Chem. Int. Ed., 2005, 7852 – 7872
Philippot et al. C.R Chimie, 2003, 1019–1034
IL are good media for the stabilization of MNP
Silveira et al. Chem. Eur. J. 2004, 10, 3734-3740
But no predictive synthesis of resulting size of MNP
D) Interest of metal nanoparticles (MNP)
Ionic liquid size (nm)BMIMPF6 2.6+/-0.4
BMIMBF4 2.5+/-0.4BMIMOTf 1.9+/-0.6
H2(4bar), 75°C
18h, ILRu(COD)(COT) Ru(NP)
34
Molecular dynamics of RMIMPF6 (R=CnH2n+1MIMPF6)
EMIMPF6 (n=2) BMIMPF6 (n=4) HMIMPF6 (n=6) OMIMPF6
(n=8)
X-Ray Diffraction of RMIMCl
D) IL generates microphase segregation
Canongia Lopes et al. J. Phys. Chem, 2006, 110, 3330-3335
Triolo et al. J. Phys. Chem, 2007, 110, 4641-4644
NNCH3
H
CnH2n+1
H H
Cl-max
2Q
L
35
D) Solvation of polar and nonpolar substrates in IL
Nonpolar substrates in nonpolar domains of IL
Polar substrates in polar domains of IL
Canongia Lopes et al.J. Phys. Chem, 2006, 110, 16816-16818
Hexane BMIMPF6 in BMIMPF6
Molecular Dynamics
and calorimetry
Jiang et al. J. Phys. Chem., 2007, 111, 4812-4818
OMIMNO3 H20 (20% mole) H20 (50% mole) H20 (80% mole)
36
D) Crystal Growth of RuNP in IL
Hypothesis : Ru(COD)(COT) is nonpolar
1) preferentially dissolved in nonpolar domains
2) local concentration increases when n increases
Ru
37
D) Crystal Growth of RuNP in IL
Hypothesis : Ru(COD)(COT) is nonpolar
Question : Control of RuNP size by microphase segregation ?
Study : Crystal growth of RuNP in various IL
Parameters : 1) Influence of temperature
2) Influence of stirring
3) Influence of the alkyl chain length
38
D) Synthesis of RuNP in BMIMNTf2 (n=4)
H2(4bar)
Stirring, 25°CBMIMNTf2
Ru(COD)(COT) Ru(NP)
0 1 2 3 4 50
10
20
30
40
50
60
70
Dis
trib
utio
n
Mean size (nm)
2.4 0.4nm
Gutel et al. J. Mat. Chem., 2007, 17, 3290-3292
39
D) Synthesis of RuNP in BMIMNTf2 (n=4) + COA
H2(4bar)
Stirring, 25°CBMIMNTf2
Ru(COD)(COT) + COA (1eq) Ru(NP)
12nm
BMIMNTf2 + COA swelling of nonpolar domains
Synthesis of RuNP in BMIMNTf2 / COA
RuNP : 7 nm
Instead
of 2.4 nmRu(COD)(COT)
dissolves preferentially in
nonpolar domains
40
0,5 1,0 1,5 2,0 2,5 3,0 3,50
10
20
30
40
50
60
70
80
Dis
tribu
tion
Mean size (nm)
25°C2.4+/-0.3nm
0°C0.9+/-0.4nm
D) Influence of temperature in BMIMNTf2 (n=4)
Gutel et al. J. Mat. Chem., 2007, 17, 3290-3292
Temperature decreases
RuNP size decreases
H2(4bar)
Stirring, TBMIMNTf2
Ru(COD)(COT) Ru(NP)
41
D) Influence of stirring in BMIMNTf2 (n=4)
0,0 0,5 1,0 1,5 2,0 2,50
10
20
30
40
50
60
70
80
dist
ribut
ion
mean size (nm)
BMIMNTf2, 0°C, stirred
BMIMNTf2, 0°C, unstirred
Presence of stirring
RuNP size similar
RuNP agglomerated
Gutel et al. J. Mat. Chem., 2007, 17, 3290-3292
H2(4bar)
0°CBMIMNTf2
Ru(COD)(COT) Ru(NP)
Stirred1.1+/-0.2nm
unstirred0.9+/-0.4nm
42
D) Conclusion of RuNP in BMIMNTf2
1) The crystal growth takes place in nonpolar domains of IL
2) The control of RuNP size is more efficient when 3D organization is more
maintained
Influence of the alkyl chain length at 0°C and in absence of stirring
43
D) Influence of alkyl chain length at 0°C, unstirred
0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,00
5
10
15
20
25
30
Dis
tribu
tion
Mean size (nm)
1 2 3 4 50
5
10
15
20
25
30
35
40
Dis
tribu
tion
Mean size (nm)
0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,00
10
20
30
40
50
60
70
Dis
tribu
tion
mean size (nm)
1 2 3 4 50
10
20
30
40
50
Dis
trib
utio
n
Mean size (nm)
Aggregation
EMIMNTf2 (n=2)2.30.6nm
BMIMNTf2
n=41.10.2nm
HMIMNTf2
n=61.90.6nm
OMIMNTf2
n=82.30.8nm
DMIMNTf2
n=10
Gutel et al. Angew. Chem. Int. Ed., Submitted
44
D) Influence of alkyl chain length at 0°C
Nature of IL 0°CEMIMNTf2 2.3 +/-0.6BMIMNTf2 1.1 +/- 0.2HMIMNTf2 1.9 +/-0.6OMIMNTf2 2.3 +/- 0.8
Gutel et al. Angew. Chem. Int. Ed., Submitted
0 1 2 3 4 50
10
20
30
40
50
60
70
80
Dis
trib
utio
n
Size (nm)
EMIMNTf2
BMIMNTf2
HMIMNTf2
OMIMNTf2
45
0
0,5
1
1,5
2
2,5
0 2 4 6 8 10Alkyl chain length (n carbons)
Mea
n s
ize
(nm
)
RuNP
Nonpolar domains (lit.)
N=38
N=201
N=586
D) Influence of alkyl chain length at 0°C
Polar medium
Linear crystal growthin nonpolar domains Interconnection of
nonpolar domains
46
D) The crystal growth in IL
47
CONCLUSION : IL, a non-innocent solvent
1) Ionic exchange is governed by the nature of anion and can be predicted by the Hard and Soft Acid Base theory
2) Ionic exchange modify the nature of the catalytic system and consequently the reactivity (isomerization of 2M3BN)
Ionic exchange
Na+A1- + C+A2
- C+A1- + Na+A-
Ionic
catalyst
IL
C+A-
48
CONCLUSION : IL, a non-innocent solvent
3D organisation -cation Interaction
+
Unsaturated
substrates
IL
C+A-
49
CONCLUSION : IL, a non-innocent solvent
Segregation in microdomains
Supramolecular matrix
IL
C+A- 3D organisation
50
Outlook
-cation interaction could be used for :
1) Separation of aromatics / alkanes
2) Stereoselective synthesis
IL could be used as a matrix for nanomaterials :
1) Generalization for other metal nanoparticles
2) Design of IL ANR CALIST Collaboration C2P2/LCC/LTSP/LECA
PhD student (Paul Campbell)
51
Academic Collaboration La lyonnaise des LI
NMR Mme Olivier-Bourbigou
M. Fenet (LRMN) M. Vallée
Mmes Baudouin et Lucas
Dr. Lefebvre
Mass spectrometry M. Simonato
M. Bouchu (LSM)
Microscopy (TEM)
M. Collière et Dr Philippot (LCC)
Dr Pelzer (Fritz-Haber Institut) M.Galland
Molecular dynamics M.Simonato
M. Bayard
Dr Padua (Université de Clermont-Ferrand)
Thanks
52
Thank you
Thank you !
53
D) Stabilization of RuNP in IL
N NBu Me
N
N
Bu
Me
H -NTf2
N
N
Bu
Me
H
HH
RuNP
HH
Steric stabilization Electronic stabilization (DLVO theory)
IL acts as a ligand IL is a electronic protective shell
Fonseca et al. J. Colloid Interface Sci., 2006, 301, 193–204Starkey Ott et al. J. Am. Chem. Soc , 2005, 127, 5758-5759
54
B) Hydrogenation CYD
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 1 2 3 4
Time (h)
Con
vers
ion
(%
)
BMIMNTf2 BMMIMNTf2
4Å
3,5Å
[Rh(COD)(PPh3)2][NTf2]
H2 (1.2 bar) / T IL