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, 21000 Dijon, France Email: 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, 2829-516 Caparica, Portugal Email: mnponte@fct.unl.pt and S Neuberg & A Behr Department of Biochemical and Chemical Engineering, Technische Universität Dortmund, Emil-Figge Str. 66, 44227 Dortmund, Germany Email: 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 + (0.9912 methanol + 0.0088 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). 7 10 Fig. S6 IR spectra of (n-bu 3 Sn) 3 (1,2,3-glycerate): (a) neat and (b) with CO 2. 7 1
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 ) 645.98 1123.46 613.98 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) 9.1001(4) 9.161(5) 8.7087(3) b (Å) 14.5728(6) 10.607(7) 17.6564(5) c (Å) 10.6193(4) 13.067(7) 9.7578(3) α ( ) 107.162(3) β ( ) 105.802(2) 109.138(3) 115.067(1) γ ( ) 94.867(3) Volume (Å 3 ) 1355.05(10) 1122.7(9) 1359.08(7) Z 2 1 2 ρ calc. (g/cm 3 ) 1.583 1.662 1.500 µ (mm -1 ) 1.874 1.860 1.859 F(000) 7696 560 624 Crystal size (mm 3 ) 0.30x0.13x0.05 0.45x0.30x0.08 0.25x0.23x0.10 sin(θ)/λ max (Å -1 ) 0.65 0.65 0.65 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 15210 11326 9378 R int 0.0402 0.0537 0.0235 Reflections with I 2σ(I) 3011 4750 2979 Data/restraints/ parameters 3099 / 0 / 143 4863 / 0 / 216 3046 / 0 / 182 Final R indices [I 2σ(I)] R1 a = 0.0248 R1 a = 0.0480 R1 a = 0.0164 wr2 b = 0.0575 wr2 b = 0.1214 wr2 b = 0.0420 R indices (all data) R1 a = 0.0259 R1 a = 0.0490 R1 a = 0.0172 wr2 b = 0.0580 wr2 b = 0.1223 wr2 b = 0.0423 Goodness-of-fit c on F 2 1.145 1.104 1.208 Largest difference peak and hole (e Ǻ 3 ) 1.582 and -0.662 1.785 and -1.746 0.303 and -0.421 CCDC deposition no. 889174 889176 889175 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) 2 +2.5229P] for 1, w=1/[σ 2 (Fo 2 +(0.0491P) 2 +5.4008P] for 1b, w=1/[σ 2 (Fo 2 +0.8036P] 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
Table S2 Phase equilibrium compositions (in mole fraction) and pressures, at 423 K, for CO 2 + (0.9912 methanol + 0.0088 glycerol), (b, d and c stand for bubble, dew and critical point, respectively) p/mpa x CO2 x methanol x glycerol 10.59 0.224 0.7692 0.0068 b 13.20 0.288 0.7058 0.0062 b 14.28 0.347 0.6473 0.0057 b 14.65 0.3585 0.6359 0.0056 b 15.13 0.374 0.6205 0.0055 b 15.53 0.3925 0.6022 0.0053 b 15.93 0.408 0.5868 0.0052 b 16.20 0.425 0.5700 0.0050 b 16.31 0.431 0.5640 0.0050 b 16.48 0.441 0.5541 0.0049 b 16.64 0.457 0.5382 0.0048 b 16.80 0.47 0.5254 0.0046 b 16.90 0.528 0.4679 0.0041 b 16.95 0.539 0.4570 0.0040 b 16.97 0.554 0.4421 0.0039 b 17.04 0.570 0.4262 0.0038 b 17.12 0.593 0.4034 0.0036 c 17.37 0.650 0.3469 0.0031 d 17.45 0.663 0.3340 0.0030 d 17.485 0.678 0.3192 0.0028 d 17.49 0.69 0.3073 0.0027 d 16.53 0.7235 0.2741 0.0024 d 16.49 0.739 0.2587 0.0023 d 16.47 0.752 0.2458 0.0022 d 16.44 0.765 0.2329 0.0021 d 16.42 0.82 0.1784 0.0016 d 16.5 0.874 0.1249 0.0011 d 14.35 0.883 0.1160 0.0010 d 13.36 0.896 0.1031 0.0009 d 3
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-O1 2.076(3), Sn-O2 2.092(3), Sn-C4 2.172(4), Sn-C8 2.176(4), Sn-O1 i 2.251(3), O1-C1 1.446(5), O2-C2 1.420(5), C1-C2 1.518(6), C2-C3 1.524(6), C3-O3 1.426(6), O3-H3 0.8400, C4-C7 1.517(6), C4-C6 1.530(7), C4-C5 1.535(6), C8-C11 1.524(7), C8-C9 1.529(6), C8-C10 1.529(7), C12-Cl1 1.741(6), C12-Cl3 1.758(5), C12-Cl2 1.760(6), C12-H12 1.0000, C13-Cl4 1.729(7), C13-Cl6 1.748(6), C13-Cl5 1.771(7); O1-Sn-O2 79.13(12), O1-Sn-C4 114.99(15), O2-Sn-C4 98.28(15), O1-Sn-C8 119.64(15), O2- Sn-C8 96.32(15), C4-Sn-C8 125.14(17), O1-Sn-O1 i 68.22(13), O2-Sn-O1 i 147.30(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 111.78(13), C2-O2-Sn 111.9(2), O1-C1-C2 108.3(4), O2-C2-C1 107.9(3), O2-C2-C3 112.3(4), C1-C2-C3 111.5(4), O3-C3-C2 115.2(4), C7-C4-C6 111.4(4), C7-C4-C5 110.5(4), C6-C4-C5 108.6(4), C7-C4-Sn 111.7(3), C6-C4-Sn 107.4(3), C5-C4-Sn 107.0(3), C11-C8-C9 109.9(4), C11-C8-C10 109.7(4), C9-C8-C10 109.3(4), C11-C8-Sn 113.8(3), C9-C8-Sn 105.9(3), C10-C8-Sn 108.0(3), Cl1-C12-Cl3 110.4(3), Cl1-C12-Cl2 110.5(3), Cl3-C12-Cl2 109.9(3), Cl1-C12-H12 108.6, Cl3-C12-H12 108.6, Cl2-C12-H12 108.6, Cl4-C13-Cl6 115.5(4), Cl4-C13-Cl5 109.0(3), Cl6-C13-Cl5 108.1(4), Cl4-C13-H13 108.0, Cl6-C13-H13 108.0, Cl5-C13-H13 108.0. 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-C8 123.91(6), C4-Sn1 2.1768(17) and C8-Sn1 2.1798(16) Å] and oxygen atom O1 of L 2- [O1-Sn1-C4 114.95(6), O1-Sn1-C8 120.70(6) and O1-Sn1 2.0862(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 148.06(4), O2-Sn1 2.0450(11) and Sn1-O1 i 2.2551(11) Å]. 4
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-O2 1.426(3), C1-C2 1.524(7), C1-C3 1.531(19), C2-O1 1.440(7), C4-C5 1.500(4), C4-C7 1.512(4), C4-C6 1.573(3), C4-Sn1 2.1768(17), C8-C9 1.525(2), C8-C11 1.527(2), C8-C10 1.535(3), C8-Sn1 2.1798(16), O1-Sn1 2.0862(11), O1-Sn1 i 2.2551(11), O2-Sn1 2.0450(11), Sn1-O1 i 2.2551(11); O2-C1-C2 108.3(3), O2-C1-C3 108.9(8), C2-C1-C3 110.9(8), O1-C2-C1 108.0(4), C5-C4-Sn1 110.30(16), C7- C4-Sn1 108.08(18), C6-C4-Sn(1) 108.69(15), C9-C8-Sn1 112.90(11), C11-C8-Sn1 108.79(11), C10-C8-Sn1 104.85(11), C2-O1-Sn1 112.4(3), C2-O1-Sn1 i 134.7(3), Sn1-O1-Sn1 i 111.93(4), C1-O2-Sn1 111.39(12), O2-Sn1- O1 80.09(4), O2-Sn1-C4 99.63(6), O1-Sn1-C4 114.95(6), O2-Sn1-C(8) 96.10(6), O1-Sn1-C8 120.70(6), C4-Sn1- C8 123.91(6), O2-Sn1-O1 i 148.06(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, 3.149 mmol) was added to a solution of n-bu 3 SnOCH 3 (3.036 g, 9.456 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, 9.03. Found: C, 48.16; H 9.77. 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
99.5 Bu 3 SnO 72.8 * * * 110 100 90 80 70 60 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! 29 28 27 26 25 24 23 22 21 20 19 18 17 16 15 14 13 12 11 ppm Fig. S4 13 C{ 1 H} NMR spectrum of the butyl groups (CDCl 3, 298 K). 6
solvent Bu 3 SnO 69.9 78.5 79 78 77 76 75 74 73 72 71 70 69 68 ppm DEPT-135 79 78 77 76 75 74 73 72 71 70 69 68 ppm Fig. S5 13 C{ 1 H} NMR spectrum of the glycerate group (CDCl 3, 298 K). (a) (b) Transmittance a.u. 1594 cm -1 4000,,, 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