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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
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
S1. The sodium salt of the trisulfonated triphenylphosphane (TPPTS)
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
∆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.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
∆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.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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).
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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).
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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).
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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).
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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.
Electronic Supplementary Material (ESI) for Catalysis Science and TechnologyThis journal is © The Royal Society of Chemistry 2011
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