1

Synthesis of cyclic carbonates catalysed by aluminium heteroscorpionate complexes

Supporting Information

José A. Castro-Osma,a,b Carlos Alonso-Moreno,b Agustín Lara-Sánchez,b Javier Martínez,b Michael Northa* and Antonio Oterob*

a Green Chemistry Centre of Excellence, Department of Chemistry, The University of York,

Heslington, York, YO10 5DD (UK). Fax: +44 1904-432-705; Tel: +44 1904 324-545; E-mail: michael.north@york.ac.uk

b Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, 13071 Ciudad Real, Spain, Fax: +34 926-295-318; Tel: +34 926-295-300; E-mail: Antonio.Otero@uclm.es

Contents NMR Spectra for ethylene carbonate 2a 2 Chemical ionization mass spectrum for ethylene carbonate 2a 3 NMR Spectra for propylene carbonate 2b 4 Chemical ionization mass spectrum for proplene carbonate 2b 5 NMR Spectra for styrene carbonate 2c 6 Electron ionization mass spectrum for styrene carbonate 2c 7 NMR Spectra for 1,2-butylene carbonate 2d 8 Chemical ionization mass spectrum for butylene carbonate 2d 9 NMR Spectra for 1,2-hexylene carbonate 2e 10 Chemical ionization mass spectrum for hexylene carbonate 2e 11 NMR Spectra for 1,2-decylene carbonate 2f 12 Chemical ionization mass spectrum for decylene carbonate 2f 13 NMR Spectra for 4-chlorostyrene carbonate 2g 14 Chemical ionization mass spectrum for 4-chlorostyrene carbonate 2g 15 NMR Spectra for 4-bromostyrene carbonate 2h 16 Electron ionization mass spectrum for 4-bromostyrene carbonate 2h 17 NMR Spectra for glycerol carbonate 2i 18 Electron ionization mass spectrum for glycerol carbonate 2i 19 NMR Spectra for 3-chloropropylene carbonate 2j 20 Chemical ionization mass spectrum for 3-chloropropylene carbonate 2j 21 NMR Spectra for 3-phenoxypropylene carbonate 2k 22 Electron ionization mass spectrum for 3-phenoxypropylene carbonate 2k 23 NMR Spectra for cyclohexyl carbonate 29 24 Electron ionization mass spectrum for cyclohexyl carbonate 29 25 Kinetic plots to determine the order with respect to complex 27 26 Plot of log(kobs avg) against log[27] 27 Kinetic plots to determine the order with respect to Bu4NBr 28 Plot of log(kobs avg) against log[Bu4NBr] 29 Plot showing that complex 27 (5 mol%) alone is not an active catalyst at 60 oC in propylene carbonate 30 Plot showing that Bu4NBr (5 mol%) alone is not an active catalyst at 60 oC in propylene carbonate 30

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

2

NMR Spectra for ethylene carbonate 2a in CDCl3

4.5422

64.3229

154.9957

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

3

Chemical ionization mass spectrum for ethylene carbonate 2a

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

4

NMR Spectra for propylene carbonate 2b in CDCl3

3.08

1.02

1.02

1.00

1.4928

1.5137

4.0125

4.0366

4.0404

4.0646

4.5411

4.5668

4.5683

4.5947

4.8150

4.8358

4.8567

4.8610

4.8820

4.9030

4.9061

4.9271

19.2459

70.4992

73.2499

154.6618

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

5

Chemical ionization mass spectrum for propylene carbonate 2b

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

6

NMR Spectra for styrene carbonate 2c in CDCl3

1.00

1.04

1.01

5.12

4.3317

4.3580

4.3604

4.3867

4.7926

4.8202

4.8485

5.6696

5.6962

5.7229

70.9649

76.5198

76.9440

77.3671

77.8315

125.7238

129.1661

129.5924

136.0084

154.5486

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

7

Chemical ionization mass spectrum for styrene carbonate 2c

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

8

NMR Spectra for 1,2-butylene carbonate 2d in CDCl3

2.92

2.28

1.03

1.04

1.00

0.9742

0.9928

1.0115

1.6644

1.6787

1.6830

1.6976

1.7008

1.7150

1.7187

1.7332

1.7370

1.7518

1.7553

1.7703

1.7884

1.7924

1.8065

1.8242

1.8282

1.8427

4.0363

4.0538

4.0572

4.0747

4.4777

4.4790

4.4977

4.4987

4.5185

4.5198

4.6041

4.6216

4.6367

4.6386

4.6405

4.6547

4.6583

4.6731

8.5723

27.0081

69.1269

76.8525

77.1719

77.4897

78.1350

155.2495

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9

Chemical ionization mass spectrum for butylene carbonate 2d

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10

NMR Spectra for 1,2-hexylene carbonate 2e in CDCl3

2.80

3.83

2.14

1.00

1.01

1.00

0.8808

0.9051

0.9277

4.0330

4.0570

4.0609

4.0849

4.4954

4.5218

4.5494

4.6545

4.6727

4.6791

4.6973

4.7041

4.7224

4.7291

4.7473

13.4920

22.0938

26.3257

33.4045

69.2477

76.5454

76.9339

76.9688

77.3924

154.7954

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

11

Chemical ionization mass spectrum for hexylene carbonate 2e

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

12

NMR Spectra for 1,2-decylene carbonate 2f in CDCl3

A DEPT spectrum showed that the CH2O peak was exactly coincident with the CHCl3 peak at 77 ppm

3.43

13.28

2.11

1.08

1.09

1.00

0.8406

0.8583

0.8752

4.0262

4.0443

4.0472

4.0653

4.4841

4.5013

4.5037

4.5051

4.5247

4.6469

4.6605

4.6657

4.6794

4.6845

4.6981

4.7034

4.7170

14.1681

22.7071

24.4512

29.1903

29.2251

29.3859

31.8601

33.9778

69.4871

76.8033

77.1216

77.4396

155.1895

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

13

Chemical ionization mass spectrum for decylene carbonate 2f

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

14

NMR Spectra for 4-chlorostyrene carbonate 2g in CDCl3

1.00

1.04

1.00

2.151.93

4.2866

4.3131

4.3153

4.3415

4.7914

4.8197

4.8476

5.6504

5.6769

5.7034

7.3033

7.3319

7.4142

7.4426

70.7098

76.4711

76.8937

77.0297

77.3172

127.0735

129.4437

134.5462

135.8115

154.1438

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

15

Electron ionization mass spectrum for 4-chlorostyrene carbonate 2g

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

16

NMR Spectra for 4-bromostyrene carbonate 2h in CDCl3

1.17

1.02

1.00

2.32

2.26

4.2769

4.3051

4.3317

4.7868

4.8147

4.8429

5.6306

5.6572

5.6837

7.2369

7.2648

7.2760

7.5654

7.5934

70.6958

76.5085

76.9319

77.0818

77.3553

123.8223

127.3339

132.4305

135.0218

154.2014

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

17

Chemical ionization mass spectrum for 4-bromostyrene carbonate 2h

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

18

NMR Spectra for glycerol carbonate 2i in CD3OD

0.94

1.30

1.13

1.20

1.11

1.00

3.4717

3.4825

3.5138

3.5247

3.6349

3.6442

3.6771

3.6855

3.7230

4.2817

4.3007

4.4563

4.4842

4.5115

4.7644

4.7743

4.7835

4.7935

5.2639

39.0099

39.2872

39.5650

39.8421

40.1219

60.6412

65.8117

76.9344

155.0067

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

19

Chemical ionization mass spectrum for glycerol carbonate 2i

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20

NMR Spectra for 3-chloropropylene carbonate 2j in CDCl3

2.03

1.00

1.02

1.00

3.7069

3.7194

3.7474

3.7599

3.7820

3.7996

3.8225

3.8401

4.4203

4.4394

4.5736

4.6012

4.6031

4.9557

4.9682

4.9734

4.9747

4.9832

4.9859

4.9871

4.9924

4.9957

5.0009

5.0022

5.0048

5.0134

5.0146

5.0199

5.0324

43.8660

67.0662

74.4089

76.8571

77.1751

77.4931

154.3639

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21

Chemical ionization mass spectrum for 3-chloropropylene carbonate 2j

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

22

NMR Spectra for 3-phenoxypropylene carbonate 2k in CDCl3

2.15

1.99

0.98

3.24

2.38

4.1364

4.1480

4.1715

4.1833

4.2352

4.2490

4.2703

4.2841

4.5592

4.5790

4.6343

5.0135

5.0260

5.0324

5.0397

5.0457

5.0535

5.0593

5.0654

5.0732

5.0856

6.9152

6.9413

6.9440

7.0102

7.0126

7.0350

7.0368

7.0593

7.0617

7.2776

7.2797

7.3038

7.3307

7.3557

66.1920

67.3169

74.0210

76.4688

76.8916

77.0831

77.3153

114.8798

122.0894

129.6184

154.2526

157.9551

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

23

Electron ionization mass spectrum for 3-phenoxypropylene carbonate 2k

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

24

NMR Spectra for cyclohexene carbonate 29 in CDCl3

2.27

2.17

4.15

2.00

19.2380

26.8419

75.8548

76.8466

77.1655

77.4833

155.4811

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014

25

Chemical ionization mass spectrum for cyclohexene carbonate 29

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26

Kinetic plots to determine the order with respect to complex 27 3 mol% catalyst (42 mM): run 1 3 mol% catalyst (42 mM): run 2

4 mol% catalyst (56 mM): run 1 4 mol% catalyst (56 mM): run 2

5 mol% catalyst (70 mM): run 1 5 mol% catalyst (70 mM): run 2

6 mol% catalyst (84 mM): run 1 6 mol% catalyst (84 mM): run 2

y = -0.00004x + 0.47628R² = 0.99

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000 30000

ln[1c] Time (s)

y = -0.00004x + 0.49325R² = 0.99

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000

ln[1c] Time (s)

y = -0.00006x + 0.46280R² = 0.99

-1.2

-1

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000 30000

ln[1c]

Time (s)

y = -0.00005x + 0.49604R² = 0.99

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000ln[1c] Time (s)

y = -0.00006x + 0.53318R² = 0.99

-1

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000ln[1c] Time (s)

y = -0.00006x + 0.46787R² = 0.99

-1

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000ln[1c] Time (s)

y = -0.00008x + 0.46176R² = 0.99

-1.6-1.4-1.2

-1-0.8-0.6-0.4-0.2

00.20.40.6

0 10000 20000 30000

ln[1c]

Time (s)y = -0.00007x + 0.49820

R² = 0.99

-1.2

-1

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000ln[1c] Time (s)

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27

Plot of log(kobs avg) against log[27]

y = 0.93x - 3.11R² = 0.99

-4.45

-4.35

-4.25

-4.15-1.4 -1.3 -1.2 -1.1 -1

log

(ko

bs a

vg)

log[27]

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28

Kinetic plots to determine the order with respect to Bu4NBr 3 mol% Bu4NBr (42 mM): run 1 3 mol% Bu4NBr (42 mM): run 2

4 mol% Bu4NBr (42 mM): run 1 4 mol% Bu4NBr (42 mM): run 2

5 mol% Bu4NBr (42 mM): run 1 5 mol% Bu4NBr (42 mM): run 2

6 mol% Bu4NBr (42 mM): run 1 6 mol% Bu4NBr (42 mM): run 2

y = -0.00003x + 0.43591R² = 0.99

-0.4

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0.4

0.5

0 5000 10000 15000 20000 25000 30000

ln[1c]

Time (s)

y = -0.00004x + 0.48024R² = 0.98930

-0.4

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

0.4

0.5

0 5000 10000 15000 20000 25000 30000

ln[1c]

Time (s)

y = -0.00005x + 0.47424R² = 0.99

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000 30000ln[1c] Time (s)

y = -0.00005x + 0.51690R² = 0.99

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000 30000

ln[1c] Time (s)

y = -0.00006x + 0.53318R² = 0.99

-1

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000

ln[1c]

Time (s)

y = -0.00006x + 0.48262R² = 1.00

-1

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000

ln[1c]

Time (s)

y = -0.00007x + 0.52723R² = 0.99

-1.2

-1

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000

ln[1c]

Time (s)

y = -0.00007x + 0.48636R² = 0.99

-1.2

-1

-0.8

-0.6

-0.4

-0.2

0

0.2

0.4

0.6

0 5000 10000 15000 20000 25000

ln[1c]

Time (s)

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29

Plot of log(kobs avg) against log[Bu4NBr]

y = 1.09x + 2.04R² = 0.99

0.5

0.6

0.7

0.8

0.9

-1.4 -1.3 -1.2 -1.1 -1

log

(kob

sav

g)

log [Bu4NBr]

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30

Plot showing that complex 27 (5 mol%) alone is not an active catalyst at 60 oC in propylene carbonate

Plot showing that Bu4NBr (5 mol%) alone is not an active catalyst at 60 oC in propylene carbonate

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0 2 4 6 8

conv

ersi

on %

time h

0

2

4

6

8

10

12

14

0 2 4 6 8

con

vers

ion

%

time h

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2014