Supporting Information. Palladium Complexes with Bulky Diphosphine. Synthesis of (Bio-) Adipic Acid from Pentenoic. Acid Mixtures.

Supporting Information Palladium Complexes with Bulky Diphosphine Ligands as Highly Selective Catalysts for the Synthesis of (Bio-) Adipic Acid from Pentenoic Acid Mixtures. Choon Heng Low, James D. Nobbs,* Martin van Meurs, Ludger P. Stubbs, Eite Drent, Srinivasulu Aitipamula, and Michelle H. L. Pung Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore, 627833, Leiden University, Leiden Institute of Chemistry, Gorlaeus laboratories, Einsteinweg 55, 2333 CC Leiden S1

Table of Contents Single Crystal X-ray Diffraction.... S4 NMR Spectra (Figures S1 S63).... S5 Figure S1. 1 H NMR spectrum of di(tert-butyl)phosphine borane complex... S5 Figure S2. 13 C{ 1 H} NMR spectrum of di(tert-butyl)phosphine borane complex.... S5 Figure S3. 31 P{ 1 H} NMR spectrum of di(tert-butyl)phosphine borane complex.... S6 Figure S4. 1 H NMR spectrum of di(1-adamantanyl)phosphine borane complex.... S6 Figure S5. 13 C{ 1 H} NMR spectrum of di(1-adamantanyl)phosphine borane complex.... S7 Figure S6. 31 P{ 1 H} NMR spectrum of di(1-adamantanyl)phosphine borane complex.... S7 Figure S7. 1 H NMR spectrum of ligand 3... S8 Figure S8. 13 C{ 1 H} NMR spectrum of ligand 3.... S8 Figure S9. 31 P{ 1 H} NMR ligand 3.... S9 Figure S10. 1 H NMR spectrum of trans-cyclohexane-1,2-diyldimethanol.... S9 Figure S11. 13 C{ 1 H} NMR spectrum of trans-cyclohexane-1,2-diyldimethanol.... S10 Figure S12. 1 H NMR spectrum of trans-1,2-bis(bromomethyl)cyclohexane.... S10 Figure S13. 1 H NMR spectrum of ligand 4... S11 Figure S14. 13 C{ 1 H} NMR spectrum of ligand 4.... S11 Figure S15. 31 P{ 1 H} NMR spectrum of ligand 4.... S12 Figure S16. 1 H NMR spectrum of ligand 5... S12 Figure S17. 13 C{ 1 H} NMR spectrum of ligand 5.... S13 Figure S18. 31 P{ 1 H} NMR spectrum of ligand 5.... S13 Figure S19. 1 H NMR (400 MHz, CDCl 3 ) spectrum of ligand 6.... S14 Figure S20. 13 C{ 1 H} NMR spectrum of ligand 6.... S14 Figure S21. 31 P{ 1 H} NMR spectrum of ligand 6.... S15 Figure S22. 1 H NMR spectrum of ligand 8... S15 Figure S23. 13 C{ 1 H} NMR spectrum of ligand 8.... S16 Figure S24. 31 P{ 1 H} NMR spectrum of ligand 8.... S16 Figure S25. 1 H NMR spectrum of ligand 9... S17 Figure S26. 13 C{ 1 H} NMR spectrum of ligand 9.... S17 Figure S27. 31 P{ 1 H} NMR spectrum of ligand 9.... S18 Figure S28. 1 H NMR spectrum of 9,10,11,15-tetrahydro-9,10-[3,4]furanoanthracene- 12,14-dione.... S18 Figure S29. 13 C{ 1 H} NMR spectrum of 9,10,11,15-tetrahydro-9,10- [3,4]furanoanthracene-12,14-dione... S19 Figure S30. 1 H NMR spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)-cisdimethanol... S19 Figure S31. 13 C{ 1 H} NMR spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)- cis-dimethanol.... S20 Figure S32. 1 H NMR spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)-cisbis(methylene) bis(tosylate).... S20 Figure S33. 13 C{ 1 H} NMR spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)- cis-bis(methylene) bis(tosylate).... S21 S2

Figure S34. 1 H NMR spectrum of cis-11,12-bis((di-tert-butylphosphino)methyl)-9,10- dihydro-9,10-ethanoanthracene borane complex.... S21 Figure S35. 31 P{ 1 H} NMR spectrum of cis-11,12-bis((di-tert-butylphosphino)methyl)- 9,10-dihydro-9,10-ethanoanthracene borane complex.... S22 Figure S36. 1 H NMR spectrum of ligand 10... S22 Figure S37. 13 C{ 1 H} NMR spectrum of ligand 10.... S23 Figure S38. 31 P{ 1 H} NMR spectrum of.ligand 10.... S23 Figure S39. 1 H NMR spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-transdicarboxylic acid.... S24 Figure S40. 13 C{ 1 H} NMR spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-transdicarboxylic acid.... S24 Figure S41. 1 H NMR spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)-transdimethanol... S25 Figure S42. 1 H NMR spectrum of trans-11,12-bis(bromomethyl)-9,10-dihydro-9,10- ethanoanthracene... S25 Figure S43. 13 C{ 1 H} NMR spectrum of trans-11,12-bis(bromomethyl)-9,10-dihydro- 9,10-ethanoanthracene.... S26 Figure S44. 1 H NMR spectrum of trans-11,12-bis((di-tert-butylphosphino)methyl)-9,10- dihydro-9,10-ethanoanthracene borane complex.... S26 Figure S45. 31 P{ 1 H} NMR spectrum of trans-11,12-bis((di-tert-butylphosphino)methyl)- 9,10-dihydro-9,10-ethanoanthracene borane complex.... S27 Figure S46. 1 H NMR spectrum of ligand 11... S27 Figure S47. 13 C{ 1 H} NMR spectrum of ligand 11.... S28 Figure S48. 31 P{ 1 H} NMR spectrum of ligand 11.... S28 Figure S49. 1 H NMR spectrum of Pd(4)(O 2 CCF 3 ) 2... S29 Figure S50. 13 C{ 1 H} NMR spectrum of Pd(4)(O 2 CCF 3 ) 2.... S29 Figure S51. 31 P{ 1 H} NMR spectrum of Pd(4)(O 2 CCF 3 ) 2.... S30 Figure S52. 1 H NMR spectrum of Pd(5)(O 2 CCF 3 ) 2... S30 Figure S53. 13 C{ 1 H} NMR spectrum of Pd(5)(O 2 CCF 3 ) 2.... S31 Figure S54. 31 P{ 1 H} NMR spectrum of Pd(5)(O 2 CCF 3 ) 2.... S31 Figure S55. 1 H NMR spectrum of Pd(6)(O 2 CCF 3 ) 2... S32 Figure S56. 31 C{ 1 H} NMR spectrum of Pd(6)(O 2 CCF 3 ) 2.... S32 Figure S57. 31 P{ 1 H} NMR spectrum of Pd(6)(O 2 CCF 3 ) 2.... S33 Figure S58. 1 H NMR spectrum of Pd(10)(O 2 CCF 3 ) 2... S33 Figure S59. 13 C{ 1 H} NMR spectrum of Pd(10)(O 2 CCF 3 ) 2.... S34 Figure S60. 31 P{ 1 H} NMR spectrum of Pd(10)(O 2 CCF 3 ) 2.... S34 Figure S61. 1 H NMR spectrum of Pd(11)(O 2 CCF 3 ) 2... S35 Figure S62. 13 C{ 1 H} NMR spectrum of Pd(11)(O 2 CCF 3 ) 2.... S35 Figure S63. 31 P{ 1 H} NMR spectrum of Pd(11)(O 2 CCF 3 ) 2.... S36 S3

Single Crystal X-ray Diffraction. A good quality single crystal grown from the solution crystallization was chosen under a Leica microscope and placed on a fibre needle which was then mounted on to the goniometer of the X-ray diffractometer. X-ray reflections were collected at 110 K on a Rigaku Saturn CCD area detector with graphite monochromated Mo-Kα radiation (λ = 0.71073 Å). Data were collected and processed using CrystalClear (Rigaku) software. Structure was solved by direct methods and SHELX-TL (G. M. Sheldrick, SHELXS-97 and SHELXL-97. 1997. Programs for the Solution and Refinement of Crystal Structures, University of Göttingen, Göttingen, Germany) was used for structure solution and least-squares refinement. The non-hydrogen atoms were refined anisotropically. All the H atoms were positioned geometrically and refined using a riding model. CCDC 1401992-1401995 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/conts /retrieving.html and deposited as Supporting Information. Table S1 Crystallographic data for the molecular complexes described in this paper Compound reference Pd(4)(CF 3 CO 2 ) 2 Pd(5)(CF 3 CO 2 ) 2 Pd(6)(CF 3 CO 2 ) 2 Pd(11)(CF 3 CO 2 ) 2 Chemical formula C 28 H 50 F 6 O 4 P 2 Pd C 24 H 42 F 6 O 4 P 2 Pd C 24 H 46 F 6 O 4 P 2 PdSi C 38 H 52 F 6 O 4 P 2 Pd Formula Mass 853.39 676.91 709.04 855.13 Crystal system Monoclinic Monoclinic Orthorhombic Monoclinic a/å 11.571(2) 29.181(6) 17.232(3) 11.779(2) b/å 14.669(3) 18.749(4) 11.631(2) 15.373(2) c/å 12.083(2) 16.231(3) 16.135(3) 12.107(2) α/ 90 90.00 90.00 90.00 β/ 115.56(3) 94.14(3) 90.00 118.184(2) γ/ 90 90.00 90.00 90.00 Unit cell volume/å 3 1850.1(8) 8857(3) 3234.0(11) 1932.4(5) Temperature/K 110(2) 110(2) 110(2) 110(2) Space group P21 C2/c Pna21 P21 No. of formula units per unit cell, Z 2 12 4 2 No. of reflections measured 24996 65707 12071 14635 No. of independent reflections 8918 10965 5781 9073 R int 0.0203 0.0394 0.0251 0.0214 Final R 1 values (I > 2σ(I)) 0.0293 0.0499 0.0313 0.0364 Final wr(f 2 ) values (I > 2σ(I)) 0.0643 0.1229 0.0791 0.0791 Final R 1 values (all data) 0.0297 0.0510 0.0324 0.0375 Final wr(f 2 ) values (all data) 0.0645 0.1238 0.0810 0.0801 Goodness of fit on F 2 1.149 1.232 1.082 1.073 S4

NMR Spectra Figure S1. 1 H NMR (400 MHz, CDCl 3 ) spectrum of di(tert-butyl)phosphine borane complex. Figure S2. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of di(tert-butyl)phosphine borane complex. S5

Figure S3. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of di(tert-butyl)phosphine borane complex. Figure S4. 1 H NMR (400 MHz, CDCl 3 ) spectrum of di(1-adamantanyl)phosphine borane complex. S6

Figure S5. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of di(1-adamantanyl)phosphine borane complex. Figure S6. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of di(1-adamantanyl)phosphine borane complex. S7

Figure S7. 1 H NMR (400 MHz, CDCl 3 ) spectrum of cis-1,2-bis[(di-1-adamantyl)phosphinomethyl)]cyclohexane, 3. Figure S8. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of cis-1,2-bis[(di-1-adamantyl)phosphinomethyl)]cyclohexane, 3. S8

Figure S9. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of cis-1,2-bis[(di-1-adamantyl)phosphinomethyl)]cyclohexane, 3. Figure S10. 1 H NMR (400 MHz, CDCl 3 ) spectrum of trans-cyclohexane-1,2-diyldimethanol. S9

Figure S11. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of trans-cyclohexane-1,2-diyldimethanol. Figure S12. 1 H NMR (400 MHz, CDCl 3 ) spectrum of trans-1,2-bis(bromomethyl)cyclohexane. S10

Figure S13. 1 H NMR (400 MHz, CDCl 3 ) spectrum of trans-1,2-bis((di-tert-butylphosphino)methyl)cyclohexane, 4. Figure S14. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of trans-1,2-bis((di-tert-butylphosphino)methyl)cyclohexane, 4. S11

Figure S15. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of trans-1,2-bis((di-tert-butylphosphino)methyl)cyclohexane, 4. Figure S16. 1 H NMR (400 MHz, CDCl 3 ) spectrum of (2-methylenepropane-1,3-diyl)bis(di-tert-butylphosphine), 5. S12

Figure S17. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of (2-methylenepropane-1,3-diyl)bis(di-tert-butylphosphine), 5. Figure S18. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of (2-methylenepropane-1,3-diyl)bis(di-tert-butylphosphine), 5. S13

Figure S19. 1 H NMR (400 MHz, CDCl 3 ) spectrum of bis((di-tert-butylphosphino)methyl)dimethylsilane, 6. Figure S20. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of bis((di-tert-butylphosphino)methyl)dimethylsilane, 6. S14

Figure S21. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of bis((di-tert-butylphosphino)methyl)dimethylsilane, 6. Figure S22. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 1,3-bis(di-tert-butylphosphino)propane, 8. S15

Figure S23. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of 1,3-bis(di-tert-butylphosphino)propane, 8. Figure S24. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of 1,3-bis(di-tert-butylphosphino)propane, 8. S16

Figure S25. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 1,4-bis(di-tert-butylphosphino)butane, 9. Figure S26. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of 1,4-bis(di-tert-butylphosphino)butane, 9. S17

Figure S27. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of 1,4-bis(di-tert-butylphosphino)butane, 9. Figure S28. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 9,10,11,15-tetrahydro-9,10-[3,4]furanoanthracene-12,14-dione. S18

Figure S29. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of 9,10,11,15-tetrahydro-9,10-[3,4]furanoanthracene-12,14-dione. Figure S30. 1 H NMR (400 MHz, d 6 -DMSO) spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)-cis-dimethanol. S19

Figure S31. 13 C{ 1 H} NMR (101 MHz, d 6 -DMSO) spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)-cis-dimethanol. Figure S32. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)-cis-bis(methylene) bis(tosylate). S20

Figure S33. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)-cis-bis(methylene) bis(tosylate). Figure S34. 1 H NMR (400 MHz, CDCl 3 ) spectrum of cis-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene borane complex. S21

Figure S35. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of cis-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene borane complex. Figure S36. 1 H NMR (400 MHz, CDCl 3 ) spectrum of cis-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene, 10. S22

Figure S37. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of cis-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene, 10. Figure S38. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of cis-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene, 10. S23

Figure S39. 1 H NMR (400 MHz, d 6 -DMSO) spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid. Figure S40. 13 C{ 1 H} NMR (101 MHz, d 6 -DMSO) spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid. S24

Figure S41. 1 H NMR (400 MHz, CDCl 3 ) spectrum of 9,10-dihydro-9,10-ethanoanthracene-11,12-diyl)-trans-dimethanol. Figure S42. 1 H NMR (400 MHz, CDCl 3 ) spectrum of trans-11,12-bis(bromomethyl)-9,10-dihydro-9,10-ethanoanthracene. S25

Figure S43. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of trans-11,12-bis(bromomethyl)-9,10-dihydro-9,10-ethanoanthracene. Figure S44. 1 H NMR (400 MHz, CDCl 3 ) spectrum of trans-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene borane complex. S26

Figure S45. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of trans-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene borane complex. Figure S46. 1 H NMR (400 MHz, CDCl 3 ) spectrum of trans-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene, 11. S27

Figure S47. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of trans-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene, 11. Figure S48. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of trans-11,12-bis((di-tert-butylphosphino)methyl)-9,10-dihydro-9,10- ethanoanthracene, 11. S28

Figure S49. 1 H NMR (400 MHz, CDCl 3 ) spectrum of Pd(4)(O 2 CCF 3 ) 2. Figure S50. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of Pd(4)(O 2 CCF 3 ) 2. S29

Figure S51. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of Pd(4)(O 2 CCF 3 ) 2. Figure S52. 1 H NMR (400 MHz, CDCl 3 ) spectrum of Pd(5)(O 2 CCF 3 ) 2. S30

Figure S53. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of Pd(5)(O 2 CCF 3 ) 2. Figure S54. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of Pd(5)(O 2 CCF 3 ) 2. S31

Figure S55. 1 H NMR (400 MHz, CDCl 3 ) spectrum of Pd(6)(O 2 CCF 3 ) 2. Figure S56. 31 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of Pd(6)(O 2 CCF 3 ) 2. S32

Figure S57. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of Pd(6)(O 2 CCF 3 ) 2. Figure S58. 1 H NMR (400 MHz, CDCl 3 ) spectrum of Pd(10)(O 2 CCF 3 ) 2. S33

Figure S59. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of Pd(10)(O 2 CCF 3 ) 2. Figure S60. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of Pd(10)(O 2 CCF 3 ) 2. S34

Figure S61. 1 H NMR (400 MHz, CDCl 3 ) spectrum of Pd(11)(O 2 CCF 3 ) 2. Figure S62. 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) spectrum of Pd(11)(O 2 CCF 3 ) 2. S35

Figure S63. 31 P{ 1 H} NMR (162 MHz, CDCl 3 ) spectrum of Pd(11)(O 2 CCF 3 ) 2. S36