Supplementary data

Triorganotin(IV) cation-promoted dimethyl carbonate synthesis from CO2 and methanol: Solution and solid-state characterization of an unexpected diorganotin(IV)-oxo cluster

Petr Šveca*, Hélène Catteyb, Zdeňka Růžičkováa, Josef Holubc, Aleš Růžičkaa and Laurent Plasseraudb*

a Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, CZ-532 10, Pardubice, Czech Republic.

b Institut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB), UMR CNRS 5260, UFR Sciences et Techniques, 9 allée A. Savary, BP 47870, F-21078 DIJON Cedex, France.

c Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, Husinec-Řež 1001, CZ-250 68, Řež, Czech Republic.

*Corresponding author, e-mail: lplasser@u-bourgogne.fr, petr.svec2@upce.cz

Content of the supplementary data:

Fig. S1 - General NMR numbering of LCN, n-Bu, Ph and [CB11H12]– moieties S2

Fig. S2 - Molecular structure of 6 S3

Table S1 - Selected crystallographic data of 4a, 6 and 7 S4

NMR spectra of 1, 2, 4, 5, 6 and 7 S5-S21

S1

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018

Supplementary data

Fig. S1: General NMR numbering of LCN, n-Bu, Ph and [CB11H12]– moieties

S2

Supplementary data

Fig. S2: Molecular structure of 6 (ORTEP presentation, 50% probability level). Hydrogen

atoms are omitted for clarity. Relevant interatomic distances [Å] and angles [°] are very close

to that reported for structurally related methylimidazolium and n-butylpyridinium 1-carba-

closo-dodecaborates* and are thus not included.

* A. S. Larsen, J. D. Holbrey, F. S. Tham, C. A. Reed, J. Am. Chem. Soc., 2000, 122, 7264; J.

Dymon, R. Wibby, J. Kleingardner, J. M. Tanski, I. A. Guzei, J. D. Holbrey, A. S. Larsen,

Dalton Trans., 2008, 2999.

S3

Supplementary data

Table S1: Selected crystallographic data of 4a, 6 and 7

Compound 4a 6 7

Empirical formula C38H38BF15NOSn C11H28B11N C90H220B22O16Sn10

Crystal system triclinic monoclinic triclinic

Space group P-1 C 1 2 1 P-1

a (Å) 12.0570(6) 22.693(4) 13.205(2)

b (Å) 12.2820(6) 7.2234(11) 20.512(3)

c (Å) 13.6270(12) 14.941(3) 24.8670(12)

(°) 103.857(6) 90 88.883(7)

(°) 105.667(6) 131.136(8) 88.070(6)

(°) 94.144(5) 90 87.940(11)

Z 2 4 2

V (Å3) 1866.1(2) 1844.5(6) 6726.2(14)

Dc (g.cm-3) 1.671 1.056 1.473

Crystal size (mm) 0.29 x 0.25 x 0.21 0.35 x 0.27 x 0.17 0.5 x 0.31 x 0.27

Crystal shape block prism block

(mm-1) 0.793 0.051 1.871

F(000) 942 624 2996

h; k; l range -15, 15; -15, 15; -17, 17 -29, 29; -9, 9; -19, 19 -16, 16; -24, 24; -30, 30

range (°) 25.242 - 27.500 3.062- 27.523 1.544 - 25.600

Reflections measured 38020 21921 65542

- independent (Rint) a) 7609 (0.0401) 4253 (0.0399) 24041 (0.1005)

- observed [I>2(I)] 8558 4014 16772

Parameters refined 518 215 1255

Max/min (eÅ-3) 1.326 / -0.867 0.176 / -0.192 4.058 / -3.380

GOF b) 1.116 1.024 1.163

R c) / wR c) 0.0311 / 0.0737 0.0390 / 0.0937 0.0823 / 0.2125

aRint = Σ│Fo2 - Fo,mean

2│/ΣFo2, bGOF = [Σ(w(Fo

2 - Fc2)2)/(Ndiffrs - Nparams)]½ , cWeighting scheme: w =

[σ2(Fo2) + (w1P)2 + w2P]-1, where P = [max(Fo

2) + 2Fc2], R(F) = Σ││Fo│ - │Fc││/Σ│Fo│, wR(F2) =

[Σ(w(Fo2 - Fc

2)2)/(Σw(Fo2)2)]½

S4

Supplementary data

1H NMR spectrum of starting LCN(n-Bu)2SnCl (1)

S5

Supplementary data

13C{1H} NMR spectrum of starting LCN(n-Bu)2SnCl (1)

S6

Supplementary data

119Sn{1H} NMR spectrum of starting LCN(n-Bu)2SnCl (1)

S7

Supplementary data

1H NMR spectrum of starting LCNPh2SnCl (2)

S8

Supplementary data

13C{1H} NMR spectrum of starting LCNPh2SnCl (2)

S9

Supplementary data

119Sn{1H} NMR spectrum of starting LCNPh2SnCl (2)

S10

Supplementary data

1H NMR spectrum of [LCN(n-Bu)2Sn]+[CB11H12]– (4)

S11

Supplementary data

11B{1H} NMR spectrum of [LCN(n-Bu)2Sn]+[CB11H12]– (4)

119Sn{1H} NMR spectrum of [LCN(n-Bu)2Sn]+[CB11H12]– (4)

S12

Supplementary data

13C{1H} NMR spectrum of [LCN(n-Bu)2Sn]+[CB11H12]– (4)

S13

Supplementary data

1H NMR spectrum of [LCNPh2Sn]+[CB11H12]– (5)

S14

Supplementary data

11B{1H} NMR spectrum of [LCNPh2Sn]+[CB11H12]– (5)

119Sn{1H} NMR spectrum of [LCNPh2Sn]+[CB11H12]– (5)

S15

Supplementary data

13C{1H} NMR spectrum of [LCNPh2Sn]+[CB11H12]– (5)

S16

Supplementary data

1H NMR spectrum of [BnNMe3]+[CB11H12]− (6)

S17

Supplementary data

13C{1H} NMR spectrum of [BnNMe3]+[CB11H12]− (6)

S18

Supplementary data

119Sn{1H} NMR spectrum of [(n-Bu)20Sn10O2(OMe)6(CO3)2]2+.[CB11H12]2− (7)

S19

Supplementary data

13C{1H} NMR spectrum of [(n-Bu)20Sn10O2(OMe)6(CO3)2]2+.[CB11H12]2− (7)

S20

Supplementary data

11B{1H} NMR spectrum of [(n-Bu)20Sn10O2(OMe)6(CO3)2]2+.[CB11H12]2− (7)

S21