Synthesis of 1,2-glycerol carbonate from carbon dioxide: the role of methanol in fluid phase equilibrium

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1 Electronic Supplementary Data Synthesis of 1,2-glycerol carbonate from carbon dioxide: the role of methanol in fluid phase equilibrium S Podila, L Plasseraud, H Cattey & D Ballivet-Tkatchenko* Université de Bourgogne, CNRS, UMR 6302, Institut de Chimie Moléculaire, 9, avenue Alain Savary, Dijon, France ballivet@u-bourgogne.fr and G V S M Carrera & M Nunes da Ponte REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica, Portugal mnponte@fct.unl.pt and S Neuberg & A Behr Department of Biochemical and Chemical Engineering, Technische Universität Dortmund, Emil-Figge Str. 66, Dortmund, Germany Arno.Behr@bci.tu-dortmund.de No. Contents Pg No. 1 Table S1 Crystallographic data for (1a), (1b), and (2) 2 2 Table S2 Phase equilibrium compositions (in mole fraction) and pressures, 3 at 423 K, for CO 2 + ( methanol glycerol) 3 Fig. S1 ORTEP view of the dimeric structure of tert-bu 2 Sn(1,2-glycerolate), (1b). 4 Hydrogen atoms excepted OH and CHCl 3 have been omitted for clarity. 4 X-ray structure of tert-bu 2 Sn(1,2-propanediolate) (2) 4 5 Fig. S2 ORTEP view of the dimeric structure of tert-bu 2 Sn(1,2-propanediolate), (2). 5 Hydrogen atoms have been omitted for clarity. 6 Synthesis and characterisation of (n-bu 3 Sn) 3 (1,2,3-glycerate) 5 7 Fig. S3 119 Sn{ 1 H} NMR spectrum in toluene-d 8 at 298 K. 6 8 Fig. S4 13 C{ 1 H} NMR spectrum of the butyl groups (CDCl 3, 298 K). 6 9 Fig. S5 13 C{ 1 H} NMR spectrum of the glycerate group (CDCl 3, 298 K) Fig. S6 IR spectra of (n-bu 3 Sn) 3 (1,2,3-glycerate): (a) neat and (b) with CO

2 Table S1 Crystallographic data for (1a), (1b), and (2) Compound 1a 1b 2 Empirical formula C 22 H 48 O 6 Sn 2 C 22 H 48 O 6 Sn 2.4CHCl 3 C 22 H 48 O 4 Sn 2 Formula weight (g mol -1 ) Temperature (K) 115(2) 115(2) 115(2) Crystal system Monoclinic Triclinic Monoclinic Space group P2 1 /c P 1 P2 1 /n a (Å) (4) 9.161(5) (3) b (Å) (6) (7) (5) c (Å) (4) (7) (3) α ( ) (3) β ( ) (2) (3) (1) γ ( ) (3) Volume (Å 3 ) (10) (9) (7) Z ρ calc. (g/cm 3 ) µ (mm -1 ) F(000) Crystal size (mm 3 ) 0.30x0.13x x0.30x x0.23x0.10 sin(θ)/λ max (Å -1 ) Index ranges h: -11; 11 h: -11; 11 h: -11; 8 k: -18; 18 k: -13; 13 k: -22; 22 l: -13; 13 l: -16; 17 l: -11; 12 Reflections collected R int Reflections with I 2σ(I) Data/restraints/ parameters 3099 / 0 / / 0 / / 0 / 182 Final R indices [I 2σ(I)] R1 a = R1 a = R1 a = wr2 b = wr2 b = wr2 b = R indices (all data) R1 a = R1 a = R1 a = wr2 b = wr2 b = wr2 b = Goodness-of-fit c on F Largest difference peak and hole (e Ǻ 3 ) and and and CCDC deposition no a R1=Σ( F o - F c )/Σ F o ; b wr2=[σw(f 2 o -F 2 c ) 2 /Σ[w(F 2 o ) 2 ] 1/2 where w=1/[σ 2 (Fo 2 +(0.0151P) P] for 1, w=1/[σ 2 (Fo 2 +(0.0491P) P] for 1b, w=1/[σ 2 (Fo P] for 2 where P=(Max(Fo 2.0)+2*Fc 2 )/3; c S =[Σw(F 2 o -F 2 c ) 2 /(n-p)] 1/2 (n = number of reflections. p = number of parameters). 2

3 Table S2 Phase equilibrium compositions (in mole fraction) and pressures, at 423 K, for CO 2 + ( methanol glycerol), (b, d and c stand for bubble, dew and critical point, respectively) p/mpa x CO2 x methanol x glycerol b b b b b b b b b b b b b b b b c d d d d d d d d d d d d 3

4 Fig. S1 ORTEP view of the dimeric structure of tert-bu 2 Sn(1,2-glycerolate), (1b). Hydrogen atoms excepted OH and CHCl 3 have been omitted for clarity. Selected bond lengths (Å) and angles (deg): Sn-O (3), Sn-O (3), Sn-C (4), Sn-C (4), Sn-O1 i 2.251(3), O1-C (5), O2-C (5), C1-C (6), C2-C (6), C3-O (6), O3-H , C4-C (6), C4-C (7), C4-C (6), C8-C (7), C8-C (6), C8-C (7), C12-Cl (6), C12-Cl (5), C12-Cl (6), C12-H , C13-Cl (7), C13-Cl (6), C13-Cl (7); O1-Sn-O (12), O1-Sn-C (15), O2-Sn-C (15), O1-Sn-C (15), O2- Sn-C (15), C4-Sn-C (17), O1-Sn-O1 i 68.22(13), O2-Sn-O1 i (11), C4-Sn-O1 i 96.98(14), C8- Sn-O1 i 98.24(14), C1-O1-Sn 113.0(2), C1-O1-Sn i 134.6(2), Sn-O1-Sn i (13), C2-O2-Sn 111.9(2), O1-C1-C (4), O2-C2-C (3), O2-C2-C (4), C1-C2-C (4), O3-C3-C (4), C7-C4-C (4), C7-C4-C (4), C6-C4-C (4), C7-C4-Sn 111.7(3), C6-C4-Sn 107.4(3), C5-C4-Sn 107.0(3), C11-C8-C (4), C11-C8-C (4), C9-C8-C (4), C11-C8-Sn 113.8(3), C9-C8-Sn 105.9(3), C10-C8-Sn 108.0(3), Cl1-C12-Cl (3), Cl1-C12-Cl (3), Cl3-C12-Cl (3), Cl1-C12-H , Cl3-C12-H , Cl2-C12-H , Cl4-C13-Cl (4), Cl4-C13-Cl (3), Cl6-C13-Cl (4), Cl4-C13-H , Cl6-C13-H , Cl5-C13-H Symmetry transformations used to generate equivalent atoms ( i ): 1-x, -y, 1-z. X-ray structure of tert-bu 2 Sn(1,2-propanediolate) (2) The X-ray crystallographic structure of (2) can be described as a dimeric structure based on a centrosymmetric inorganic Sn 2 O 2 four-membered ring (Fig. S2). Each tin atom is bound to two tertbutyl groups and chelated by bidentate 1,2-propanediolate ligand (L 2- ), forming a five-membered ring, characteristic of dioxastannolane compounds. One of the oxygen atoms of L 2- (O1) is coordinated to both tin atoms, with two different distances, leading to the dimeric structure. The tin atoms are pentacoordinated in a distorted trigonal bipyramid geometry. The equatorial plan includes the tert-butyl groups [C4-Sn1-C (6), C4-Sn (17) and C8-Sn (16) Å] and oxygen atom O1 of L 2- [O1-Sn1-C (6), O1-Sn1-C (6) and O1-Sn (11) Å]. Axial positions are occupied by O2 of L 2-, and O1 i from the second 1,2-propanediolate chelating ligand [O2-Sn1-O1 i (4), O2-Sn (11) and Sn1-O1 i (11) Å]. 4

5 Fig. S2 ORTEP view of the dimeric structure of tert-bu 2 Sn(1,2-propanediolate), (2). Hydrogen atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg): C1-O (3), C1-C (7), C1-C (19), C2-O (7), C4-C (4), C4-C (4), C4-C (3), C4-Sn (17), C8-C (2), C8-C (2), C8-C (3), C8-Sn (16), O1-Sn (11), O1-Sn1 i (11), O2-Sn (11), Sn1-O1 i (11); O2-C1-C (3), O2-C1-C (8), C2-C1-C (8), O1-C2-C (4), C5-C4-Sn (16), C7- C4-Sn (18), C6-C4-Sn(1) (15), C9-C8-Sn (11), C11-C8-Sn (11), C10-C8-Sn (11), C2-O1-Sn (3), C2-O1-Sn1 i 134.7(3), Sn1-O1-Sn1 i (4), C1-O2-Sn (12), O2-Sn1- O (4), O2-Sn1-C (6), O1-Sn1-C (6), O2-Sn1-C(8) 96.10(6), O1-Sn1-C (6), C4-Sn1- C (6), O2-Sn1-O1 i (4), O1-Sn1-O1 i 68.07(4), C4-Sn1-O1 i 96.10(6), C8-Sn1-O1 i 97.89(5). Symmetry transformations used to generate equivalent atoms ( i ): 1-x, -y, 1-z. Synthesis and characterisation of (n-bu 3 Sn) 3 (1,2,3-glycerate) Glycerol (0.290 g, mmol) was added to a solution of n-bu 3 SnOCH 3 (3.036 g, mmol) in 10 ml toluene in a Schlenk tube equipped with a reflux condenser. The mixture was heated at 358 K for 6 h, then cooled down to room temperature, and volatiles eliminated by trap to trap distillation. The residue is a colorless viscous oil. Anal. (%): Calcd for C 39 H 86 O 3 Sn 3 : C, 48.83; H, Found: C, 48.16; H The 119 Sn{ 1 H} and 13 C{ 1 H} NMR spectra are shown in Figs S3-S5. The reactivity with CO 2 was determined by IR spectroscopy (Fig. S6), and volumetry at room temperature and atmospheric pressure according to a published procedure (Ballivet-Tkatchenko D, Douteau O & Stutzmann S, Organometallics, 19 (2000) 4563). 5

6 99.5 Bu 3 SnO 72.8 * * * ppm * impurities; integrated area ratio = 1.8 for 99.5 and 72.8 resonances Fig. S3 119 Sn{ 1 H} NMR spectrum in toluene-d 8 at 298 K. C # C $ Sn-CH 2 -CH 2 -CH 2 -CH 3! " # $% C! Bu 3 SnO C " C # C $ C " C! ppm Fig. S4 13 C{ 1 H} NMR spectrum of the butyl groups (CDCl 3, 298 K). 6

7 solvent Bu 3 SnO ppm DEPT ppm Fig. S5 13 C{ 1 H} NMR spectrum of the glycerate group (CDCl 3, 298 K). (a) (b) Transmittance a.u cm ,,, 89,, 8,,, )9,, ),,, 49,, 4,,, 9, 500 ;<=>?@AB>C!DAE4 Fig. S6 IR spectra of (n-bu 3 Sn) 3 (1,2,3-glycerate): (a) neat and (b) with CO 2.!"#$"%&%'()%& 7