supporting information supramolecularly controlled surface
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Supporting Information
Supramolecularly Controlled Surface Activity of an
Amphiphilic Ligand. Application to Aqueous Biphasic
Hydroformylation of Higher Olefins
Natacha Six,a Antonella Guerriero,b David Landy,c Maurizio Peruzzini,b Luca
Gonsalvi,*b Frédéric Hapiot*a and Eric Monflier
a
a Université Lille Nord de France, CNRS UMR 8181, Unité de Catalyse et de Chimie du Solide, UCCS
UArtois, Faculté Jean Perrin, rue Jean Souvraz, SP18, F-62300 Lens, France.
Tel: (+) 33(0)321791772 ; Fax: (+) 33(0)321791755 ; E-mail: [email protected] b
Tel: (+) 39 055 5225251; Fax: (+) 39 055 5225203; E-mail: [email protected]
Istituto di Chimica del Composti Organometallici, Consiglio Nazionale delle Ricerche (ICCOM-CNR), Via
Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze, Italy.
c
Université Lille Nord de France, UCEIV, Université du Littoral 145, Avenue Maurice Schumann, MREI 1,
F-59140 Dunkerque, France
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Index
S1. The sodium salt of the trisulfonated triphenylphosphane (TPPTS).
S2. Job plot derived from chemical shift variations of the phosphorous signal on 31P NMR
spectra of β-CD/1 mixtures in D2
S3. Job plot derived from chemical shift variations of the tBu signal on
O at 25 °C.
1H NMR spectra of β-
CD/1 mixtures in D2
S4. Job plot derived from chemical shift variations of the tBu signal on
O at 80 °C.
1H NMR spectra of
RAME-β-CD/1 mixtures in D2
S5. Job plot derived from chemical shift variations of the tBu signal on
O at 25 °C.
1H NMR spectra of
RAME-β-CD/1 mixtures in D2
S6. 2D T-ROESY NMR spectrum of an equimolar mixture of native β-CD and 1 (10 mM/10
mM) at room temperature in D
O at 80 °C.
2
S7. 2D T-ROESY NMR spectrum of an equimolar mixture of native β-CD and 1 (10 mM/10
mM) at 80 °C in D
O (mixing time = 300 ms).
2
S8. Zoom of S6 on dipolar contacts between the tBu protons of 1 and CD protons H-3, H-5 and H-6.
O (mixing time = 300 ms).
S9. 2D T-ROESY NMR spectrum of an equimolar mixture of RAME-β-CD and 1 (10 mM/10
mM) at room temperature in D2
S10. Zoom of S8 on dipolar contacts between the tBu protons of 1 and CD protons H-3, H-5
and H-6.
O (mixing time = 300 ms).
S11. 2D T-ROESY NMR spectrum of an equimolar mixture of RAME-β-CD and 1 (10
mM/10 mM) at 80 °C in D2
S12. Zoom of S10 on dipolar contacts between the tBu protons of 1 and CD protons H-3, H-5
and H-6.
O (mixing time = 300 ms).
S13. Basicity of 1.
S14. Reaction profiles of entries 5, 6, 8 and 9.
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S1. The sodium salt of the trisulfonated triphenylphosphane (TPPTS)
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0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
∆δ (
1)·[1
]
r = [1]/([1] + [β-CD])
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
S2. Continuous variation plot (Job plot) derived from chemical shift variations of the
phosphorous signal on 31P NMR spectra of β-CD/1 mixtures in D2
O at 25 °C. The total
concentration of species is 10 mM.
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∆δ (
1)·[1
]
r = [1]/([1] + [β-CD])
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.000 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
S3. Continuous variation plot (Job plot) derived from chemical shift variations of the tBu
signal on 1H NMR spectra of β-CD/1 mixtures in D2
O at 80 °C. The total concentration of
species is 10 mM.
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∆δ (
1)·[1
]
r = [1]/([1] + [RAME-β-CD])
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.000 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
S4. Continuous variation plot (Job plot) derived from chemical shift variations of the tBu
signal on 1H NMR spectra of RAME-β-CD/1 mixtures in D2O at 25 °C. The total
concentration of species is 10 mM.
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0,00
0,05
0,10
0,15
0,20
0,25
0,30
0,35
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
∆δ (
1)·[1
]
r = [1]/([1] + [RAME-β-CD])
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.000 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
S5. Continuous variation plot (Job plot) derived from chemical shift variations of the tBu
protons signal on 1H NMR spectra of RAME-β-CD/1 mixtures in D2O at 80 °C. The total
concentration of species is 10 mM.
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S6. 2D T-ROESY NMR spectrum of an equimolar mixture of native β-CD and 1 (10 mM/10
mM) at room temperature in D2O (mixing time = 300 ms).
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S7. 2D T-ROESY NMR spectrum of an equimolar mixture of native β-CD and 1 (10 mM/10
mM) at 80 °C in D2
O (mixing time = 300 ms).
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tBu
H-3H-6 H-5
H-2 H-4
S8. Zoom of S6 on dipolar contacts between the tert-Bu protons of 1 and the H-3, H-5 and H-6 CD protons of native β-CD.
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S9. 2D T-ROESY NMR spectrum of an equimolar mixture of RAME-β-CD and 1 (10 mM/10
mM) at room temperature in D2
O (mixing time = 300 ms).
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tBu
CD protons
S10. Zoom of S8 on dipolar contacts between the tBu protons of 1 and CD protons H-3, H-5 and H-6.
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S11. 2D T-ROESY NMR spectrum of an equimolar mixture of RAME-β-CD and 1 (10
mM/10 mM) at 80 °C in D2O (mixing time = 300 ms).
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tBu
H-3H-6 H-5
H-2 H-4
S12. Zoom of S10 on dipolar contacts between the tBu protons of 1 and CD protons H-3, H-5
and H-6.
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S13. Determination of the phosphane basicity
Phosphane selenides were synthesized by stirring overnight at room temperature excess
selenium (10 equiv.) with 1 (250 mg) in absolute ethanol (15 mL) under nitrogen. The
resulting mixture was directly analyzed by 31P{1H} NMR without any purification. NMR
spectra exhibit the presence of phosphane selenides characterized by a singlet with two
satellites due to only 7.6% of active selenium isotope (77Se) in NMR spectroscopy. The
upfield phosphorus signal (-83.09 ppm) was characteristic of the PTA phosphorus atom. The
first order phosphorus-selenium coupling constants (1JP-Se) of the Se=1 selenide allowed for
the estimation of the basicity of 1. The higher the 1JP-Se value, the lower the basicity. Ligand 1
(1JP-Se = 814.6 Hz) was thus more basic than the previously synthesized CD non-interacting
phosphane N-Bz-PTA (Scheme 1) for which a 1JP-Se
= 817.7 Hz constant was determined.
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S14. Reaction profiles of entries 5, 6, 8 and 9.
Experimental conditions: Rh(acac)(CO)2 (4.07 × 10-2 mmol), water-soluble ligand (0.21 mmol), cyclodextrin (0.48 mmol), H2O (11.5 mL), 1-alkene (20.35 mmol), 1500 rpm, CO/H2
(1/1): 50 bar, 6 h. Entry 5: 80 °C without CD; Entry 6: 80 °C with RAME-β-CD; Entry 8: 100 °C without CD; Entry 9: 100 °C with RAME-β-CD.
The reaction profiles of these four relevant experiments highlight the poisoning effect of RAME-β-CD at 80 °C (red arrow) and the increase in activity observed at 100 °C (blue arrow).
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011