Supplementary Information for: Synthesis of Non-Symmetrically Sulphonated Phosphine Sulphonate Based Pd(II) Catalyst Salts for Olefin Polymerisation Reactions Timo M. J. Anselment a, Carly E. Anderson a and Bernhard Rieger a M. Bele Boeddinghaus b, Thomas F. Fässler b a Dipl.-Chem. Univ. T. M. J. Anselment, Dr. C. E. Anderson, Prof. Dr. Dr. h.c. B. Rieger, WACKER-Lehrstuhl für Makromolekulare Chemie der Technischen Universität München, Lichtenbergstr. 4, 85747 Garching bei München, Germany. Fax: +49.89.289-13562; Tel: +49.89.289-13571; E-mail: rieger@tum.de. b Dipl.-Chem. Univ. M. B. Boeddinghaus, Prof. Dr. T. F. Fässler, Lehrstuhl für Anorganische Chemie mit Schwerpunkt Neue Materialien der Technischen Universität München, Lichtenbergstr. 4, 85747 Garching bei München, Germany.
1. NMR spectra for newly synthesised compounds 1.1 [K] 2 [rac-o,m-triphenylphosphine disulphonate] (rac-o,m-tppds) 2b 1 H NMR (5 MHz, D 2 O) δ 8.6 (m, 1H), 7.82 (m, 1H), 7.7 (m, 1H), 7.51 (m, 1H), 7.41 (m, 2H), 7.37 7.29 (m, 3H), 7.26 (m, 3H), 7.4 (m, 1H). 31 P NMR (121 MHz, D 2 O) δ -1.5 13 C{ 1 H} NMR (75 MHz, D 2 O) δ 148.2 (d, J(C-P) = 26.2 Hz), 143.7 (d, J(C-P) = 6.4 Hz), 139.6 (d, J(C-P) = 12.8 Hz), 137.1 (d, J(C-P) = 1.3 Hz), 137. (d, J(C-P) = 7.9 Hz), 136.9 (s), 134.7 (s), 134.5 (d, J (C-P)= 21.8 Hz), 134.4 (s), 132.3 (s), 131. (s), 13.8 (s), 13.7 (s), 13.2 (s), 13.2 (d, J(C-P) = 5.9 Hz), 129.8 (d, J(C-P) = 7. Hz), 128.3 (d, J(C-P) = 4.7 Hz), 126.7 (s). 1 H NMR (5 MHz, D 2 O, water suppression)
-1.16-1.52 1E+5-1.16-1.52 1E+5 1E+5 1E+5 9 9 8 7 8 2b 6 7 5 6 4 5 3 4 2 2c 2a 1 3 2 6 5 4 3 2 1 f1 (ppm) -1 3b -2-3 -4-5 -6-7 -8-9 6.99 1. 1.31-1 -12-14 -16-1 1 2.35 6.99 1. 1.31-1 5 45 4 35 3 25 2 15 1 5 f1 (ppm) -5-1 -15-2 -25-3 -35-4 -45-5 31 P { 1 H} NMR (121 MHz, D 2 O) 13 C{ 1 H} NMR (75 MHz, D 2 O)
1.2 [Na] 3 [o,m,m-triphenylphosphine trisulphonate] (o,m,m-tppts) 2c 1 H NMR (5 MHz, D 2 O) δ 8.9 (m, 1H), 7.89 7.85 (m, 2H), 7.73 7.69 (m, 2H), 7.61 (m, 1H), 7.55 (m, 2H), 7.49 7.42 (m, 3H), 7.14 (m, 1H). 31 P NMR (121 MHz, D 2 O) δ -1.3 13 C{ 1 H} NMR (75 MHz, D 2 O) δ 148.1 (d, J (C-P) = 26.5 Hz), 143.7 (d, J (C-P) = 6.4 Hz), 138.8 (d, J (C-P) = 13. Hz), 137.3 (d, J (C-P) = 19.2 Hz), 137.1 (d, J (C-P) = 1.3 Hz), 133.7 (d, J (C-P) = 21.7 Hz), 132.5 (s), 131. (d, J (C-P) = 2.6 Hz), 13.8 (s), 13.3 (d, J (C-P) = 6.2 Hz), 128.3 (d, J (C-P) = 4.9 Hz), 127. (s). 1 H NMR (5 MHz, D 2 O, water suppression)
2c 2b 3c 31 P { 1 H} NMR (121 MHz, D 2 O) 13 C{ 1 H} NMR (75 MHz, D 2 O)
1.3 1-(3-Sulphonatophenyl)-1H-9-thia-1-phosphaanthracene-9.9.1-trioxide 4, sodium salt 1 H NMR (5 MHz, D 2 O) δ 8.17 (m, 2H), 8.5 8.1 (m, 2H), 7.98 (m, 2H), 7.91 (m, 2H), 7.76 (m, 2H), 7.67 (m, 2H), 7.57 7.48 (m, 2H). 13 C{ 1 H} NMR (75 MHz, D 2 O) δ 144.7 (d, J(C-P) = 13.6 Hz), 141.3 (d, J(C-P) = 7.6 Hz), 135.3 (s), 135.2 (d, J(C-P) = 11.5 Hz), 134.8 (d, J(C-P) = 11.9 Hz), 134. (d, J(C-P) = 4.9 Hz), 132.2 (d, J(C-P) = 113.7 Hz), 131.5 (s), 13.9 (d, J(C-P) = 13.5 Hz), 129.1 (d, J(C-P) = 12.8 Hz), 128.9 (d, J(C-P) = 12. Hz), 126.3 (d, J(C-P) = 7.5 Hz). 31 P{ 1 H} NMR (121 MHz, D 2 O) δ 8.9 (s). 1 H NMR (5 MHz, D 2 O, water suppression)
31 P { 1 H} NMR (121 MHz, D 2 O) 13 C{ 1 H} NMR (75 MHz, D 2 O)
1.4 [K(18-crown-6)] 2 [rac-o,m-tppds] 5b 1 H NMR (3 MHz, CD 2 Cl 2 ) δ 8.9 (m, 1H), 7.95 (m, 1H), 7.76 (m, 1H), 7.35 7.15 (m, 8H), 7.1 7.3 (m, 2H), 3.53 (s, 57H). 13 C NMR (75 MHz, CD 2 Cl 2 ) δ 152.8 (d, J(C-P) = 27.3 Hz), 147.7 (d, J(C-P) = 7.9 Hz), 139.9 (d, J(C-P) = 14.2 Hz), 139.5 (d, J(C-P) = 16.7 Hz), 136.1 (d, J(C-P) = 2.5 Hz), 135. (d, J(C-P) = 23.5 Hz), 134.6 (d, J(C-P) = 11.7 Hz), 134. (d, J(C-P) = 19.4 Hz), 131.7 (d, J(C-P) = 29.2 Hz), 129.4 (s), 128.8 (s), 128.4 (d, J(C-P) = 6.1 Hz), 128.2 (s), 128.1 (d, J(C-P) = 3.6 Hz), 128. (d, J(C-P) = 6.1 Hz), 126.4 (s), 7.4 (s). 31 P NMR (121 MHz, CD 2 Cl 2 ) δ -9.3 (s). 1 H NMR (3 MHz, CD 2 Cl 2 )
5b 31 P { 1 H} NMR (121 MHz, CD 2 Cl 2 ) 13 C{ 1 H} NMR (75 MHz, CD 2 Cl 2 )
1.5 [K(18-crown-6)][o-TPPMS] 5a 1 H NMR (3 MHz, CD 2 Cl 2 ) δ 8.11 (m, 1H), 7.42 7.15 (m, 12H), 7.4 (m, 1H), 3.56 (s, 27H). 13 C{ 1 H} NMR (75 MHz, CD 2 Cl 2 ) δ 152.7 (d, J(C-P) = 27.1 Hz), 139.9 (d, J(C-P) = 14.5 Hz), 135.9 (d, J(C-P) = 2.4 Hz), 135. (d, J(C-P) = 23.2 Hz), 134.2 (s), 133.9 (s), 129.4 (s), 128.9 (s), 128.5 (d, J(C-P) = 6.1 Hz), 128.3 (s), 128. (d, J(C-P) = 5.1 Hz), 7.5 (s). 31 P{ 1 H} NMR (121 MHz, CD 2 Cl 2 ) δ -9. (s). 1 H NMR (3 MHz, CD 2 Cl 2 )
31 P { 1 H} NMR (121 MHz, CD 2 Cl 2 ) 13 C{ 1 H} NMR (75 MHz, CD 2 Cl 2 )
1.6 [K(18-crown-6)] 2 [κ 2 (P,O){rac-o,m-TPPDS}] 6 1 H NMR (5 MHz, CD 2 Cl 2 ) δ 8.7 (m, 1H), 8.3 (m, 1H), 7.94 (m, 1H), 7.64 (m, 2H), 7.46 (m, 2H), 7.36 (m, 5H), 7.6 (m, 1H), 3.54 (s, 48H),.53 (d, 3 J (H-P) = 3.2 Hz, 3H). 13 C NMR (75 MHz, CD 2 Cl 2 ) δ 15.1 (d, J(C-P) = 14. Hz), 148.4 (d, J(C-P) = 1.5 Hz), 135.6 (d, J(C-P) = 1.5 Hz), 135.5 (s), 135.4 (d, J(C-P) = 11.9 Hz), 135.4 135.2 (m), 132. 131.5 (m), 131.3 (d, J(C-P) = 13.4 Hz), 131.3 13.8 (m), 131. (d, J(C-P) = 2.6 Hz), 13.8 (d, J(C-P) = 2.1 Hz), 13.7 129.8 (m), 13.2 (d, J(C-P) = 6.4 Hz), 129. 128.9 (m), 128.9 128.8 (m), 128.4 128.3 (m), 128.2 (d, J(C-P) = 3.6 Hz). 31 P NMR (121 MHz, CD 2 Cl 2 ) δ +27.4..53.53 8 24 75 23 8.8 8.8 8.7 8.6 8.4 8.2 7.95 7.93 7.66 7.64 7.63 7.62 7.48 7.47 7.45 7.44 7.41 7.4 7.38 7.37 7.35 7.34 7.32 7.8 7.6 7.4 4 38 36 34 32 3 7 65 6 55 22 21 2 19 18 28 5 17 26 24 22 2 18 16 14 45 4 35 3 16 15 14 13 12 12 25 11 1.8.97 1.6 2.1 2.16 5.25.97 1 8 6 4 2-2 2 15 1 5 1 9 8 7 6 8.15 8.1 8.5 8..48 2.1 7.95 2. 7.9 7.85 1.9 7.8 1.8 7.75 7.7 1.7 7.65 7.6 7.55 f1 (ppm) 1.6 1.5 7.5 7.45 1.4 7.4 1.3 7.35 7.3 1.2 7.25 7.2 7.15 1.1 1. f1 (ppm) 7.1 7.5.9 7..8 6.95.7 3.15 3..6.5.4.3.2.1. -5 5 4 3 2 1 1.8.97 1.6 2.1 13.97 2.16 5.25.97 51.88.48 3.15 3. -1 8. 7.5 7. 6.5 6. 5.5 5. 4.5 4. f1 (ppm) 3.5 3. 2.5 2. 1.5 1..5.
27.39 14 13 12 11 1 9 8 7 6 5 4 3 2 1 5 45 4 35 3 25 2 15 f1 (ppm) 1 5-5 -1-15 -2 31 P { 1 H} NMR (121 MHz, CD 2 Cl 2 ) 7.48 1.28 65 15.18 149.99 148.46 148.46 148.32 148.32 135.57 135.55 135.45 135.29 131.96 131.96 131.52 131.35 131.17 131.1 13.98 13.83 13.76 13.73 13.63 13.63 13.23 13.14 13.9 128.92 128.92 128.77 128.77 128.31 128.31 128.17 8 6 75 7 65 6 55 55 5 5 45 4 35 3 25 45 4 2 15 35 1 5 3 15 149 148 147 146 145 144 143 142 141 14 139 138 f1 (ppm) 137 136 135 134 133 132 131 13 129 128-5 25 2 15 1 5 15 14 13 12 11 1 9 8 f1 (ppm) 7 6 5 4 3 2 1 13 C{ 1 H} NMR (75 MHz, CD 2 Cl 2 )
1.7 [K(18-crown-6)][κ 2 (P,O){o-TPPMS}] 7 1 H NMR (3 MHz, CD 2 Cl 2 ) δ 8. (m, 1H), 7.55 7.18 (m, 12H), 6.91 (m, 1H), 3.47 (s, 24H),.44 (d, 3 J (H- P) = 3.4 Hz, 3H). 13 C NMR (75 MHz, CD 2 Cl 2 ) δ 15.1 (d, J (C-P) = 14. Hz), 135.3 (d, J (C-P) = 1.4 Hz), 134.9 (d, J (C-P) = 12.5 Hz), 131.6 (d, J (C-P) = 52.5 Hz), 13.9 (d, J (C-P) = 2.4 Hz), 13.8 (d, J (C-P) = 2.1 Hz), 13.4 (d, J (C- P) = 41. Hz), 13. (d, J (C-P) = 6.3 Hz), 128.8 (d, J (C-P) = 11. Hz), 128.3 (d, J (C-P) = 7.5 Hz), 7.5 (s), - 2.5 (s). 31 P NMR (121 MHz, CD 2 Cl 2 ) δ +26.6. 32 3 28 26 24 22 2 18 16 14 12 1 8 6 4 2.98 12.21 1. 24.41 2.82 8.1 8.1 8.9 8.8 8.7 8.7 8.6 8.6 7.53 7.42 7.41 7.39 7.39 7.3 7.3 7.1 7. 6.98 6.97 3.55.52.51-2 8.5 8. 7.5 7. 6.5 6. 5.5 5. 4.5 4. f1 (ppm) 3.5 3. 2.5 2. 1.5 1..5. -.5 1 H NMR (3 MHz, CD 2 Cl 2 )
26.89 6.92 32 3 28 26 24 22 2 18 16 14 12 1 8 6 4 2-2 45 4 35 3 25 2 15 1 f1 (ppm) 5-5 -1-15 -2 31 P { 1 H} NMR (121 MHz, CD 2 Cl 2 ) 13 C{ 1 H} NMR (75 MHz, CD 2 Cl 2 )
2. Polymer analysis 2.1 Selected GPC data 2.1.1 Polyethylene The depicted GPC plots show a representative behaviour of the synthesised polyethylene with observed bimodal distribution of molecular weights. Multi detection was employed to facilitate separate processing of the high and low molecular weight traces.
PE of Entry 9 in Table 3:
RI only detection: 2.1.2 GPC plot of an AN/ethene copolymerisation (Entry 16)
2.2 High temperature 1 H-NMR spectroscopic assignment for the AN/ethene copolymerisation (Entry 16)