Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006

Transcription

1 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006

2 Importance of Interfacial Adsorption in the Biphasic Hydroformylation of Higher Olefins Promoted by Cyclodextrins: A Molecular Dynamics Study at the Decene Water Interface N. Sieffert and G. Wipff* Laboratoire MSM, UMR CNRS 7177, Institut de Chimie 4 rue B. Pascal, Strasbourg (France) wipff@chimie.u-strasbg.fr - 1 / 23 -

3 Figure 3 : Simulation box containing one [RhH(CO)(TPPTS 3 )] 9- complex immersed in the aqueous phase, with Na + as counterions (in cyan ; system B3) and definition of the X, Y, and Z axis. - 2 / 23 -

4 Final snapshots a Density b <S> c Decene A1 Z (Å) Z (Å) Water Figure 4 : Neat decene water interface. Solvents are shown separately on two lines for clarity. a. After 2 ns of MD. b. In kg.dm -3 in function of the z-direction (Å) of the box, averages over the last 500 ps of MD. c. Order parameter <S> of decene and water as a function of the z-position (see text for definition). - 3 / 23 -

5 D1 - decene CD A1 - decene Figure 5 : Zoom view on an uncomplexed decene molecule (system A1) and a decene molecule complexed to CD (system D1) with selected surrounding solvent molecules (A full version of this figure is given in Figure S3). - 4 / 23 -

6 t = 0 ns a t = 8 ns a Density b B1 Rh(acac)(CO)2 B2 Na3L B3 [RhH(CO)L3] 9- Figure 6 : Rh(acac)(CO) 2 complexes (system B1), TPPTS 3- ligands L (system B2) and the [RhH(CO)(TPPTS) 3 ] 9- precatalyst (system B3) at the decene water interface. a. Initial and final snapshots (only one solvent is represented for clarity). b. Density curves (kg.dm -3 ) of the solvents and the solute (without Na + counterions) as a function of the z-position (in Å) measured over the last 3 ns of MD. - 5 / 23 -

7 t = 0 ns t = 8 ns Distance from the interface a B4 [RhH(CO)L2] 6- B5 [RhH(CO)2L2] 6- B6 [RhH(CO)L2 (decene)] 6- Figure 7 : Rhodium complexes at the decene water interface. (a) Distance (Å) between the Rh atom and the interface. - 6 / 23 -

8 B6 [RhH(CO)L2(decene) D4 [RhH(CO)L2(decene) CD B5 [RhH(CO)2L2 B4 [RhH(CO)L2 D1 - decene CD Figure 8 : The [RhH(CO)(TPPTS) 2 ] 6-, [RhH(CO) 2 (TPPTS) 2 ] 6-, [RhH(CO)(TPPTS) 2 (decene)] 6-, decene CD and [RhH(CO)(TPPTS) 2 (decene)] 6- CD complexes adsorbed at the decene water interface (systems B4, B5, B6, D1 and D4, respectively). - 7 / 23 -

9 Side view d Density c t = 10 ns b t = 0 ns a Figure 9 : Eight free CD s at the interface (system C1). Only decene (a) or water (b) is represented for clarity. Initial (a) and final (b) snapshots. (c) Density curves of the solvents and the solute calculated during the last 3 ns of MD. (d) XY view of the simulation box (solvents hidden for clarity). - 8 / 23 -

10 t = 0 ns t = 5 ns Distance from the interface D1 Decene D2 Undecanal D3 RhH(CO)2L2 D4 Intermediate Figure 10 : Cyclodextrin complexes at the decene water interface. Distances between the interface and decene (yellow), undecanal (orange), CD (green) and Rh complexes (blue). Water is hidden for clarity. - 9 / 23 -

11 H H H H H H H H H H H H H H H H H H H H Figure S1 : Atomic charges on the 1-decene. Charges on C and H atoms are shown separately for clarity / 23 -

12 A3 TIP5P / 50 atm A2 TIP3P / 50 atm A1 TIP3P / 1 atm Figure S2 : Distribution of life time of decene molecules in slabs of z = ± 2 Å (left), ± 4 Å (middle) and ± 8 Å (right) centred on the Gibbs dividing surface / 23 -

13 Without CD a With CD Distance (Å) e Order parameter (S) d N( H 2 O) around C 1 c snapshot b Figure S3 : Interfacial behavior of 1-decene, with and without CD. a. One decene molecule arbitrary selected. b. The selected decene molecule is represented in yellow whereas the surrounding decene molecules (up to 12 Å from C 1 ) are in brown. Water molecules within 5 Å from C 1 are in red and those up to 12 Å are in blue. c. Number of H 2 O molecules within 5 Å from the C 1 atom as a function of time (ps). d. Order parameter as a function of time (see text for details). e. Distance between C 1 and the interface / 23 -

14 Figure S4 : Smoothed trajectory of a decene molecule exchanging between the interface and the bulk decene. Cumulated view over the last 0.5 ns of MD. Other decene molecules are hidden and water is not cumulated for clarity (System A1) / 23 -

15 Final snapshots a Density b <S> c A1 350 K - 1 atm / TIP3P A2 350 K - 50 atm / TIP3P A3 350 K - 50 atm / TIP5P Figure S5 : The decene water interface simulated using different water models and different pressures. a. After 2 ns of MD. b. In kg.dm 3 in function of the z-direction (Å) of the box calculated over the last 0.5 ns of MD. c. Order parameter as a function of the z-position (in Å; see text for details) / 23 -

16 t = 0 ns t = 8 ns Distance from the interface B6 TIP5P B6 TIP3P Figure S6 : The [RhH(CO)(TPPTS) 2 (decene)] 6- reaction intermediate at the interface comparing two models of water: the TIP3P model in system B6 and the TIP5P model in system B / 23 -

17 C1 C1 Unconstrained MD Constrained MD Side view d Density c t = 10 ns b t = 0 ns a Figure S7 : 8 CD s at the interface either unconstrainded (system C1) or constrained to remain open (system C1 ). Only decene (a) or water (b) is represented for clarity. Initial (a) and final (b) snapshots. (c) density curves (kg.dm -3 ) of the solvents and the solute taken calculated during the last 3 ns of MD. (d) XY view of the simulation box (solvents hidden for clarity) / 23 -

18 DG = kj.mol -1 DG, kj.mol -1 d(o g C methyl ), Å Figure S8 : Free energy profile for decomplexation of the decene CD complex at the interface, obtained by PMF calculation. Initial and final snapshots and free energy profile (kj.mol -1 ) as a function of the O g C methyl distance (Å). See text for details / 23 -

19 External Intermediate Internal Figure S9 : Snapshots of the decene CD complex at the decene water interface showing different configurations of the guest inside the CD cavity (system D1) / 23 -

20 Figure S10 : Solvation of 1-decene complexed by CD at the decene water interface (system D1). Radial distribution functions of O water and H water atoms around the terminal (C 1 ) atom of decene. Averages over the last 0.5 ns of MD / 23 -

21 External Bent Internal Figure S11 : Snapshots of the undecanal CD complex at the decene water interface showing different configurations of the guest inside the CD cavity (system D2) / 23 -

22 t = 5 ns t = 0 ns Figure S12 : Snapshots of the facial complexes between [RhH(CO)(TPPTS) 2 (decene)] 6- and CD at the beginning (0 ns; structure prepared by a MD simulation in the gas phase at 300 K) and the end (5 ns) of the dynamics at 350 K (system D4) / 23 -

23 t = 5 ns t = 0 ns Figure S13 : Snapshots of the facial complexes between [RhH(CO) 2 (TPPTS) 2 ] 6- and CD at the beginning (0 ns) and the end (5 ns) of the dynamics (system D3) / 23 -

24 Up to 3 Å Up to 4 Å Up to 5 Å Figure S14 : Number of =C(H 2 ) carbon atoms of decene molecules around the Rh atom of the [RhH(CO)(TPPTS) 2 ] 6- catalyst, using three different cut-off values (system B4) / 23 -