Air-Stable (Phenylbuta-1,3-diynyl)palladium(II) Complexes: Highly Active Initiators for Living Polymerization of Isocyanides

Supporting Information Air-Stable (Phenylbuta-1,3-diynyl)palladium(II) Complexes: Highly Active Initiators for Living Polymerization of Isocyanides Ya-Xin Xue, Yuan-Yuan Zhu, Long-Mei Gao, Xiao-Yue He, Na Liu, Wu-Yi Zhang, Jun Yin, Yunsheng Ding, Hongping Zhou, and Zong-Quan Wu, * Department of Polymer Science and Engineering, School of Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei 230009, China College of Chemistry and Chemical Engineering, Key Laboratory of Functional Inorganic Materials Chemistry of Anhui Province, Anhui University, Hefei 230039, China S1

Instruments S3 Materials S3 Synthetic procedures for Pd complexes 1a g S4-S10 Typical polymerization procedure of 2 with 1a d S10 Typical procedure used to grow poly(phenyl isocyanide)s of various M n S11 Typical procedure for block copolymerization S11 Typical kinetic study of the polymerization of 2 with 1a d S12 Table S1. Polymerization results of 2 with 1f and 1g as initiators S12 References S13 Figure S1 S13 Figure S2-6: FT-IR, 1 H, 13 C, 31 P NMR and UV-vis spectra of poly-a2 100 S14-S16 Figure S7-9: SEC chromatograms of the polymer of 2 S16-S17 Figure S10-15: Time-dependent SEC and plots of M n -conversion for the polymerization of 2 with 1b-d S18-S20 Figure S16-21: SEC chromatograms and plots of M n and M w /M n with initial feed ratios of monomer to initiator for the polymerization of 2 with 1f and 1g S21-S23 Figure S22-46: FT-IR, 1 H and 13 C NMR spectra of compound 1-7 S24-S36 Figure S47-54: 1 H NMR spectra of monomer 3a-f and 4 S36-S40 Figure S55-60: 1 H NMR spectra of the polymers of 3a-e and 4 S40-S43 Figure S61-62: 1 H NMR spectra of the polymers of 2 initiated by 1f and 1g S43-S44 S2

Instruments. The 1 H, 13 C and 31 P NMR spectra were recorded using a Bruker 600 MHz, 400 MHz or 300 MHz spectrometer. Size exclusion chromatography (SEC) was performed on Waters 1515 pump and Waters 2414 differential refractive index (RI) detector (set at 40 C) using a series of linear Styragel HR1, HR2 and HR4 columns. Molecular weight and polydispersity data are reported relative to polystyrene standards. The eluent was tetrahydrofuran (THF) at a flow rate of 0.3 ml/min. FT-IR spectra were recorded on Perkin-Elmer Spectrum BX FT-IR system using KBr pellets. UV-vis spectra were performed on a UNIC 4802 UV/VIS double beam spectrophotometer in 1.0 cm length quartz cell. Circular dichroism (CD) spectra were obtained in a 1.0 mm quartz cell at 25 C using a JASCO J815 or J1500 spectropolarimeter. The polymer concentration was calculated on the basis of the monomer units and was 0.2 mg/ml. The optical rotations were measured in a 5.0 cm quartz cell on a JASCO P-1030 polarimeter. Melting points were obtained with a Mel-Temp apparatus and are uncorrected. X-ray diffraction data of single crystals were collected on a Siemens Smart 1000 CCD diffractometer. The determination of unit cell parameters and data collections were performed with Mo-Ka radiation (l = 0.71073 A ). Unit cell dimensions were obtained with least-squares refinements and all structures were solved by direct methods using SHELXS-97. The other nonhydrogen atoms were located in successive difference Fourier syntheses. The final refinement was performed using full-matrix least-squares methods with anisotropic thermal parameters for non-hydrogen atoms on F2. The hydrogen atoms were added theoretically and riding on the concerned atoms. Materials All solvents were purified by the standard procedures before use. THF was further dried over sodium S3

benzophenone ketyl, distilled onto LiAlH 4 under nitrogen, and distilled under high vacuum just before use. 1-Ethynyl-4-methylbenzene, 1-ethynyl-4-methoxybenzene, 1-ethynylbenzene, 1-ethynyl-4-fluorobenzene, ethynyltrimethylsilane, 1,4-diethynylbenzene, 1,3,5-triethynylbenzene, trans-dichlorobis(triethylphosphine)palladium(ii), copper(i) iodide, copper(i) chloride, N-bromosuccinimide, and AgNO 3 were purchased from Aladdin and Sigma-Aldrich, and were used as received without further purification. Isocyanide monomers 2, 1 3a, 2 3b, 3c, 3 3d, 4 3e, 5 3f 6 and diisocyanide 4 7 were prepared according to the literatures and the structures were confirmed by 1 H NMR. Synthetic Procedures for Pd Complexes 1a g. Synthesis of 5a: To a solution of 1-ethynyl-4-methylbenzene (1.16 g, 10.0 mmol) in acetone (50 ml) were added NBS (1.96 g, 11 mmol) and AgNO 3 (170 mg, 1.0mmol) at room temperature with magnetic stirring. After 1 h, the reaction mixture was diluted with n-hexane (100 ml) and the solid was filtered off. The filtrate was concentrated under reduced pressure and passed through a pad of silica gel using n-hexane as an eluent. The filtrate was collected and evaporated under reduced pressure to afford 1-(2-bromoethynyl)-4-methylbenzene 5a as yellowish oil (1.85 g, 95%). 1 H NMR (600 MHz, CDCl 3, 25 C) δ 7.35 (d, J = 8.1 Hz, 2H, aromatic), 7.15 (d, J = 8.1 Hz, 2H, aromatic), 2.35 (s, 3H, CH 3 ). Synthesis of 6a: A mixture of 5a (0.42 g, 2.15 mmol), CuI (20.0 mg, 0.10 mmol), and Pd(PPh 3 ) 2 Cl 2 (0.12 g, 0.10 mmol) in a 50 ml three-neck flask was degassed and re-filled with N 2. After this procedure S4

was repeated three times, triethylamine (15 ml) and ethynyltrimethylsilane (0.60 ml, 4.30 mmol) were added with syringe. The reaction solution was stirred at 55 C for 6 h, then the solvent was evaporated to dryness under reduced pressure, and the residue was further purified by column chromatography with petrol ether as the eluent to afford 6a as colorless liquid (0.35 g, 86%). 1 H NMR (300 MHz, CDCl 3, 25 C): δ 7.38 (d, J = 8.1 Hz, 2H, aromatic), 7.12 (d, J = 7.8 Hz, 2H, aromatic), 2.35 (s, 3H, Ph CH 3 ), 0.22 (s, 9H, TMS). Compounds 6b, 6c, and 6d were prepared under the similar procedure as described for 6a by using 1-ethynyl-4-methoxybenzene, 1-ethynylbenzene, and 1-ethynyl-4-fluorobenzene as start materials. 6b: 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.43 (d, J = 8.4 Hz, 2H, aromatic), 6.83 (d, J = 9.0 Hz, 2H, aromatic), 3.81 (s, 3H, OCH 3 ), 0.23 (s, 9H, TMS). 6c: 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.49 (d, J = 7.2 Hz, 2H, aromatic), 7.38 7.35 (m, 1H, aromatic), 7.32 (t, J = 7.8 Hz, 2H, aromatic), 0.24 (s, 9H, TMS). 6d: 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.47 (d, J = 8.4 Hz, 2H, aromatic), 7.01 (d, J = 8.4 Hz, 2H, aromatic), 0.23 (s, 9H, TMS). Synthesis of 7a: To a solution of 6a (0.20 g, 0.94 mmol) in dichloromethane (30 ml) and methanol (30 S5

ml) was added K 2 CO 3 (0.78 g, 5.66 mmol). After the mixture was stirred at room temperature for 1 h, the solvent was evaporated under reduced pressure. The residue was extracted with ether and the organic phase was washed successively with H 2 O (15 ml 3) and brine (15 ml 3). The organic layer was dried over Na 2 SO 4. After filtration and evaporation, the resulting crude product was purified by column chromatography with petrol ether as eluent to afford 7a as a white solid (0.13 g, 97%). 1 H NMR (300 MHz, CDCl 3, 25 C): δ 7.41 (d, J = 8.1 Hz, 2H, aromatic), 7.13 (d, J = 7.8 Hz, 2H, aromatic), 2.46 (s, 1H, CH), 2.36 (s, 3H, CH 3 ). FT-IR (KBr, cm 1 ): 2960 (ν C H, aromatic), 2926 (ν C H, aromatic), 2856 (ν C H, aromatic), 2203 (ν C C ), 2105 (ν C C ). Compounds 7b, 7c, and 7d were prepared using the similar procedure. These materials were unstable in air and were used directly for next step without further characterization. Synthesis of 1a. Compound 7a (25.0 mg, 0.18 mmol) was treated with trans-dichlorobis(triethylphosphine)palladium (74.0 mg, 0.18 mmol) in the presence of copper(i) chloride (2.5 mg, 0.025 mmol) as catalyst in 15 ml of diethylamine and dichloromethane (v/v =1/1). The mixture was stirred at room temperature for 1 h. After the solvent was removed by evaporation under reduced pressure, the residue was purified by chromatography with petrol ether as eluent. The crude product was recrystallized from petrol ether and methanol to afford 1a as a white solid (60 mg, 65%). M.P.: 126.8 127.9 C. 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.34 (d, J = 8.1 Hz, 2H, aromatic), 7.07 (d, J = 7.8 Hz, 2H, aromatic), 2.32 (s, 3H, CH 3 Ph), 1.99 1.94 (m, 12H, PCH 2 CH 3 ), 1.21 1.16 (m, 18H, PCH 2 CH 3 ). 13 C NMR (150 MHz, CDCl 3, 25 C): δ 137.57, 131.92, 128.76, 120.29, 95.69, 88.98, S6

76.47, 70.25, 21.30, 15.18, 15.09, 15.00, 8.10. 31 P NMR (121.5 MHz, CDCl 3, 25 C): δ 18.8. FT-IR (KBr, cm 1 ): 2961 (ν C H, aromatic), 2931 (ν C H, aromatic), 2876 (ν C H, aromatic), 2179 (ν C C ), 2057 (ν C C ), 1727 (ν C=C, aromatic), 1648 (ν C=C, aromatic). MS m/z calcd for C 23 H 37 ClP 2 Pd [M] + : 516.11; Found: 516.13. Anal. Calcd (%) for C 23 H 37 ClP 2 Pd: C, 53.40; H, 7.21; Found (%): C, 53.42; H, 7.24. Compounds 1b, 1c, and 1d were synthesized according to the similar procedure from the reaction of 7b, 7c and 7d with trans-dichlorobis(triethylphosphine)palladium in dichloromethane, respectively. 1b: M.P.: 97.1 98.6 C. 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.39 (d, J = 9.0 Hz, 2H, aromatic), 6.80 (d, J = 9.0 Hz, 2H, aromatic), 3.80 (s, 3H, OCH 3 ), 1.99 1.94 (m, 12H, PCH 2 CH 3 ), 1.22 1.17 (m, 18H, PCH 2 CH 3 ). 13 C NMR (150 MHz, CDCl 3, 25 C): δ 159.20, 133.67, 115.66, 113.84, 95.21, 89.14, 75.94, 70.23, 55.24, 15.29, 8.26. 31 P NMR (121.5 MHz, CDCl 3, 25 C): δ 18.8. FT-IR (KBr, cm 1 ): 2963 (ν C H, aromatic), 2919 (ν C H, aromatic), 2851 (ν C H, aromatic), 2178 (ν C C ), 2060 (v C C ), 1739 (ν C=C, aromatic), 1602 (ν C=C, aromatic). MS m/z calcd for C 23 H 37 ClOP 2 Pd [M] + : 532.10; Found: 532.07. Anal. Calcd (%) for C 23 H 37 ClOP 2 Pd: C, 51.79; H, 6.99; Found (%): C, 51.77; H, 7.02. 1c: M.P.: 114.7 116.2 C. 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.45 7.44 (m, 2H, aromatic), 7.27 7.26 (m, 3H, aromatic), 1.99 1.94 (m, 12H, PCH 2 CH 3 ), 1.22 1.17 (m, 18H, PCH 2 CH 3 ). 13 C NMR (150 MHz, CDCl 3, 25 C): δ 132.40, 128.27, 127.80, 123.76, 96.86, 89.22, 77.45, 70.42, 15.40, 8.40. 31 P NMR (121.5 MHz, CDCl 3, 25 C): δ 18.8. FT-IR (KBr, cm 1 ): 2962 (ν C H, aromatic), 2918 (ν C H, aromatic), 2868 (ν C H, aromatic), 2189 (ν C C ), 2069 (v C C ), 1740 (ν C=C, aromatic), 1587 (ν C=C, aromatic). S7

MS m/z calcd for C 22 H 35 ClP 2 Pd [M] + : 502.09; Found: 502.11. Anal. Calcd (%) for C 22 H 35 ClP 2 Pd: C, 52.50; H, 7.01; Found (%): C, 52.48; H, 7.05. 1d: M.P.: 119.7 121.3 C. 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.43 7.40 (m, 2H, aromatic), 6.96 (t, J = 8.4 Hz, 2H, aromatic), 1.99 1.94 (m, 12H, PCH 2 CH 3 ), 1.22 1.16 (m, 18H, PCH 2 CH 3 ). 13 C NMR (150 MHz, CDCl 3, 25 C): δ 163.09, 161.44, 134.21, 119.87, 115.61, 96.96, 89.06, 69.30, 15.42, 8.42. 31 P NMR (121.5 MHz, CDCl 3, 25 C): δ 18.8. FT-IR (KBr, cm 1 ): 2955 (ν C H, aromatic), 2925 (ν C H, aromatic), 2851 (ν C H, aromatic), 2179 (ν C C ), 2057 (v C C ), 1740 (ν C=C, aromatic), 1593 (ν C=C, aromatic). MS m/z calcd for C 22 H 34 ClFP 2 Pd [M] + : 520.08; Found: 520.10. Anal. Calcd (%) for C 22 H 34 ClFP 2 Pd: C, 50.69; H, 6.57; Found (%): C, 50.65; H, 6.60. Synthesis of 1e: Compound 7c (25.0 mg, 0.20mmol) was treated with 1c (100.0 mg, 0.20mmol) in the presence of copper(i) chloride (5.0 mg, 0.050 mmol) as catalyst in 15 ml of diethylamine and dichloromethane (v/v = 1/1). The mixture was stirred at room temperature for 1 h. After the solvent was removed by evaporation under reduced pressure, the residue was purified by chromatography with petrol ether as eluent. The crude product was recrystallized from petrol ether and methanol to afford 1e as a white solid (88 mg, 75%). M.P.: 180.9 181.5 C. 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.46 7.44 (m, 4H, aromatic), 7.28 7.27 (m, 6H, aromatic), 2.06 2.02 (m, 12H, PCH 2 CH 3 ), 1.25 1.19 (m, 18H, PCH 2 CH 3 ). 13 C NMR (150 MHz, CDCl 3, 25 C): δ 132.21, 128.09, 127.44, 123.97, 111.83, 92.83, 77.62, 69.77, 16.95, 9.50. 31 P NMR (121.5 MHz, CDCl 3, 25 C): δ 18.8. FT-IR (KBr, cm 1 ): 2967 (ν C H, S8

aromatic), 2920 (ν C H, aromatic), 2852 (ν C H, aromatic), 2179 (ν C C ), 2049 (v C C ), 1737 (ν C=C, aromatic), 1588 (ν C=C, aromatic). MS m/z calcd for C 32 H 40 P 2 Pd [M] + : 592.16; Found: 592.10. Anal. Calcd (%) for C 32 H 40 P 2 Pd: C, 64.81; H, 6.80; Found (%): C, 64.78; H, 6.84. Synthesis of 1f: 1,4-Diethynylbenzene (16.0 mg, 0.13mmol) was treated with trans-dichlorobis(triethylphosphine)palladium (0.14 g, 0.34mmol) in the presence of copper(i) chloride (3.6 mg, 0.019) as catalyst in the mixture of diethylamine (8 ml) and dichloromethane (8 ml). The reaction solution was stirred at room temperature for 1 h. After the solvent was removed by evaporation under reduced pressure, the residue was purified by chromatography with petrol ether and dichloromethane as the eluent (v/v = 1/1) to afford 1f as a yellow solid (86 mg, 77% yield). M.P.: 121.3 122.5 C. 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.12 (s, 4H, aromatic), 1.97 1.94 (m, 24H, PCH 2 CH 3 ), 1.23 1.14 (m, 36H, PCH 2 CH 3 ). 13 C NMR (150 MHz, CDCl 3, 25 C): δ 130.34, 125.03, 106.71, 96.07, 15.39, 8.31. 31 P NMR (121.5 MHz, CDCl 3, 25 C): δ 17.9. FT-IR (KBr, cm 1 ): 2962 (ν C H, aromatic), 2919 (ν C H, aromatic), 2848 (ν C H, aromatic), 2120 (ν C C ), 1737 (ν C=C, aromatic), 1727 (ν C=C, aromatic). MS m/z calcd for C 34 H 64 Cl 2 P 4 Pd 2 [M] + : 878.14; Found: 878.10. Anal. Calcd (%) for C 34 H 64 Cl 2 P 4 Pd 2 : C, 46.38; H, 7.33; Found (%): C, 46.34; H, 7.37. S9

Synthesis of 1g: 1,3,5-Triethynylbenzene (16.0 mg, 0.11 mmol) was treated with trans-dichlorobis(triethylphosphine)palladium (0.14 g, 0.34 mmol) in the presence of 3.6 mg of copper(i) chloride as catalyst in the mixture of diethylamine (8 ml) and dichloromethane (8 ml). The mixture was stirred at room temperature for 1 h. After the solvent was removed by evaporation under reduced pressure, the residue was purified by chromatography with petrol ether and dichloromethane as the eluent (v/v = 1/1) to afford 1g as a yellow solid (95 mg, 70 %). M.P.: 141.9 143.3 C. 1 H NMR (600 MHz, CDCl 3, 25 C): δ 6.93 (s, 3H, aromatic), 1.97 1.94 (m, 36H, PCH 2 CH 3 ), 1.23 1.14 (m, 54H, PCH 2 CH 3 ). 13 C NMR (150 MHz, CDCl 3, 25 C): δ 130.49, 127.46, 106.25, 95.15, 15.50, 8.43. 31 P NMR (121.5 MHz, CDCl 3, 25 C): δ 17.9. FT-IR (KBr, cm 1 ): 2969 (ν C H, aromatic), 2924 (ν C H, aromatic), 2875 (ν C H, aromatic), 2098 (ν C C ), 1748 (ν C=C, aromatic), 1646 (ν C=C, aromatic). MS m/z calcd for C 48 H 93 Cl 3 P 6 Pd 3 [M] + : 1278.19; Found: 1278.2. Anal. Calcd (%) for C 48 H 93 Cl 3 P 6 Pd 3 : C, 44.98; H, 7.31; Found (%): C, 44.95; H, 7.35. Typical Polymerization Procedure of 2 With 1a d (poly-a2 100 ): A 10 ml oven-dried flask was charged with monomer 2 (100 mg, 0.35 mmol), THF (1.64 ml) and a stir bar. To this stirring solution was added a solution of 1a in THF (0.035 M, 0.10 ml) via a microsyringe at ambient temperature. The concentrations of monomer 2 and catalyst 1a were 0.2 and 0.002 M, respectively ([2] 0 /[1a] 0 = 100). The S10

reaction flask was then immersed into an oil bath at 55 C and stirred for 10 h. After cooled to room temperature, the polymerization solution was precipitated into a large amount of methanol, collected by centrifugation, and dried in vacuum at room temperature overnight (96 mg, 96% yield). SEC: M n = 2.9 10 4, M w /M n = 1.11. 1 H NMR (600 MHz, CDCl 3, 25 C): δ 7.07 7.42 (br, aromatic), 3.08 4.08 (br, OCH 2 ), 0.87 1.70 (br, CH 2 and CH 3 ). 13 C NMR (150 MHz, CDCl 3, 25 C): δ 164.96, 162.56, 150.35, 129.63, 127.27, 117.04, 64.90, 31.89, 29.62, 29.44, 29.34, 28.63, 26.00, 22.67, 14.05. 31 P NMR (121.5 MHz, CDCl 3, 25 C): δ 14.4. FT-IR (KBr, cm 1 ): 2950 (ν C H, aromatic), 2925 (ν C H, aromatic), 2851 (ν C H, aromatic), 2173 (ν C C ), 1721 (ν C=O ), 1599 (ν C=N ). Typical Procedure Used to Grow Poly(phenyl isocyanide)s of Various Molecular Weights from Palladium Complex 1a d. Under an atmosphere of nitrogen, various amount of palladium complex 1a in THF ([1a] 0 = 0.20 M) were added via a microsyringe to a series of solutions of isocyanide monomer 2 (50 mg, 0.17mmol) in THF. The concentrations of 2 and 1a were 0.2 and 0.002 M, respectively. Each of the reaction mixtures were then stirred for 10 h at 55 C and quenched by the addition of a large amount of methanol, collected by centrifugation, washed with methanol, and dried under vacuum to afford polymers. The M n and M w /M n of these polymers were characterized by SEC. Typical Procedure for Block Copolymerization (Poly(a2 100 -b-2 100 )). Poly-a2 100 (20.0 mg, M n = 2.9 10 4, M w /M n = 1.11) and monomer 2 (20.0 mg, 70.0mmol) were placed in a dry ampule, which was then evacuated on a vacuum line and flushed with dry nitrogen. After the evacuation-flush procedure had been repeated three times, a three-way stopcock was attached to the ampule, and dry THF (1.40 ml) was added by a syringe. The mixture was then stirred under a dry nitrogen atmosphere and immersed into an oil bath at 55 C for further 10 h. After cooled to room temperature, the polymerization solution S11

was precipitated into a large amount of methanol, collected by centrifugation, and dried in vacuum at room temperature overnight (38 mg, 95% yield). SEC: M n = 5.8 10 4, M w /M n = 1.07. Typical Kinetic Study of the Polymerization of 2 with 1a d. A mixture monomer 2 (100.0 mg, 0.35 mm) and a standard polystyrene (M n = 2630, 50.0 mg for 1a, 25.0 mg for 1b d) were placed in a dry ampule, which was then evacuated on a vacuum line and flushed with dry nitrogen. After the evacuation-flush procedure had been repeated three times, a three-way stopcock was attached to the ampule, and dry THF (1.36 ml) was added by a syringe. To this was added a solution of 1a in THF (10 µm, 0.39 ml) via a microsyringe at ambient temperature. The concentrations of 1a and 2 were 0.0022 and 0.2 M, respectively. The mixture was then stirred under a dry nitrogen atmosphere and heated to 55 C ([2] 0 = 0.2 M, [2] 0 /[1a] 0 = 90). The conversion of 2 was followed by measuring the SEC of the reaction mixture at appropriate time intervals. The peak area of the unreacted 2 relative to that of the internal standard (PSt) was used for the determination of the conversion of 2 on the basis of the linear calibration curve. The M n and M w /M n were estimated by SEC and reported as equivalent to standard polystyrene. Table S1. Polymerization Results of 2 with 1f and 1g as Initiator at 55 C ([2] 0 = 0.2 M). a Run Initiator b [2] 0 /[1] 0 Polymer c M n c M w /M n Yield d 1 1f 30 poly-f2 30 8.9 10 3 1.17 97% 2 1f 40 poly-f2 40 1.2 10 4 1.19 95% 3 1f 60 poly-f2 60 1.5 10 4 1.19 85% 4 1g 20 poly-g2 20 7.5 10 3 1.16 98% 5 1g 30 poly-g2 30 9.8 10 3 1.18 98% 6 1g 45 poly-g2 45 1.2 10 4 1.20 97% a The polymers was synthesized according to Scheme 4 in main text. b The initial feed ratio of [2] 0 /[1f] 0 and [2] 0 /[1g] 0. c The M n and M w /M n were determined by SEC and reported as equivalent to standard polystyrene. d Isolated yield. S12

References 1. Wu, Z.-Q.; Ono, R. J.; Chen, Z.; Bielawski, C. W. J. Am. Chem. Soc. 2010, 132, 14000. 2. Onitsuka, K.; Yamamoto, M.; Mori, T.; Takei, F.; Takahashi, S. Organometallics 2006, 25, 1270. 3. Wu, Z.-Q.; Radcliffe, J. D.; Ono, R. J.; Chen, Z.; Li, Z.; Bielawski, C. W. Polym. Chem. 2012, 3, 874. 4. Wu, Z.-Q.; Qi, C.-G.; Liu, N.; Wang, Y.; Yin, J.; Zhu, Y.-Y.; Qiu, L.-Z.; Lu, H.-B. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2939. 5. Hertlera, K. R.; Corey, E. J. J. Org. Chem. 1958, 23, 1221. 6. Takei, F.; Yanai, K.; Onitsuka, K.; Takahashi, S. Chem. Eur. J. 2000, 6, 983. 7. Wu, Z.-Q.; Liu, D.-F.; Wang, Y.; Liu, N.; Yin, J.; Zhu, Y.-Y.; Qiu, L.-Z.; Ding, Y.-S. Polym. Chem. 2013, 4, 4588. 8. Wu, Z.-Q.; Nagai, K.; Banno, M.; Okoshi, K.; Onitsuka, K.; Yashima, E. J. Am. Chem. Soc. 2009, 131, 6708. Figure S1. Thin layer chromatography analysis of purified 7a with petroleum ether as eluent (a) and after deposit at ambient temperature for 2 days with petroleum ether (b) and with petroleum ether and ethyl acetate in 3/1 volume ratio (c) as eluent (Developed under UV light at 254 nm). S13

3000 2000 1000 Wavenumber (cm -1 ) Figure S2. FT-IR spectrum of poly-a2 100 at 25 C using KBr pellets. Figure S3. 1 H NMR spectrum of poly-a2 100 in CDCl 3 at 25 C (600 MHz). S14

Figure S4. 13 C NMR spectrum of poly-a2 100 in CDCl 3 at 25 C (150 MHz). Figure S5. UV-vis spectrum of poly-a2 100 measured at 25 C using KBr pellets. S15

Normalized intensity (a. u.) 1a poly-a2 50 40 30 20 10 0-10 δ/ppm Figure S6. 31 P NMR spectra of 1a and the corresponding poly-a2 50 in CDCl 3 at 25 C (121.5 MHz). Normalized intensity (a. u.) poly-a2 50 (t) poly-a2 100 (t) 20 22 24 26 28 30 Retention time (min) Figure S7. SEC chromatograms of poly-a2 50 (t) and poly-a2 100 (t) prepared by using 1a as initiator in toluene at 55 C. S16

Normalized intensity (a. u.) poly-a2 50 (c) poly-a2 100 (c) 20 22 24 26 28 30 Retention time (min) Figure S8. SEC chromatograms of poly-a2 50 (c) and poly-a2 100 (c) prepared by using 1a as initiator in CHCl 3 at 55 C. Normalized intensity (a. u.) poly-a2 50 (a) poly-a2 50 (d) 20 22 24 26 28 30 32 Retention time (min) Figure S9. SEC chromatograms of poly-a2 50 (a) and poly-a2 50 (d) prepared by using 1a as initiator in acetone and DMF at 55 C. S17

PSt 2 0 h 1 h poly-b2 m 2.5 h poly-b2 m 5 h 25 30 35 Retention time (min) Figure S10. SEC chromatograms for the polymerization of 2 with 1b as catalyst in THF at 55 C with PSt as internal standard measurement at different time intervals. ([2] 0 = 0.2 M, [2] 0 /[1b] 0 = 75). 20 3 M n (kda) 10 2 M w /M n 0 0 20 40 60 80 100 Conversion (%) 1 Figure S11. Plot of M n and M w /M n values as a function of conversion of 2 with 1b as initiator in THF at 55 C ([2] 0 = 0.2 M, [2] 0 /[1b] 0 = 75). S18

PSt 2 0 h 4.2 h poly-c2 m 7.7 h poly-c2 m poly-c2 m 10.5 h 25 30 35 Retention time (min) Figure S12. SEC chromatograms for the polymerization of 2 with 1c as initiator in THF at 55 C with PSt as internal standard measurement at different time intervals ([2] 0 = 0.2 M, [2] 0 /[1c] 0 = 75). 20 3 M n (kda) 10 2 M w /M n 0 0 20 40 60 80 100 Conversion (%) 1 Figure S13. Plot of M n and M w /M n values as a function of conversion of 2 with 1c as initiator in THF at 55 C ([2] 0 = 0.2 M, [2] 0 /[1c] 0 = 75). S19

PSt 2 0 h 2.6 h poly-d2 m 5.2 h poly-d2 m poly-d2 m 13.3 h 25 30 35 Retention time (min) Figure S14. SEC chromatograms for the polymerization of 2 with 1d as initiator in THF at 55 C with PSt as internal standard measurement at different time intervals ([2] 0 = 0.2 M, [2] 0 /[1d] 0 = 110). 30 M n (kda) 20 10 3 M w /M n 2 0 0 20 40 60 80 100 Conversion (%) 1 Figure S15. Plot of M n and M w /M n values as a function of conversion of 2 with 1d as initiator in THF at 55 C ([2] 0 = 0.2 M, [2] 0 /[1d] 0 = 110). S20

Normalized intensity(a. u.) [2] 0 /[1f] 0 = 30 [2] 0 /[1f] 0 = 40 [2] 0 /[1f] 0 = 60 20 22 24 26 28 30 Retention time (min) Figure S16. SEC chromatograms of poly-f2 n prepared from 2 with 1f as initiator in THF at 55 C with 30, 40 and 60 initial feed ratios. Normalized intensity(a. u.) [2] 0 /[1g] 0 = 20 [2] 0 /[1g] 0 = 30 [2] 0 /[1g] 0 = 45 20 22 24 26 28 30 Retention time (min) Figure S17. SEC chromatograms of poly-g2 n prepared from 2 with 1g as initiator in THF at 55 C with 20, 30 and 45 initial feed ratios. S21

Normalized intensity(a. u.) M n = 6198, PDI = 1.22 M n = 8887, PDI = 1.17 M n = 11961, PDI = 1.19 M n = 13514, PDI = 1.20 M n = 14540, PDI = 1.19 18 20 22 24 26 28 Retention time (min) Figure S18. SEC chromatograms of poly-f2 n prepared from 2 with 1f as initiator in THF at 55 C with different initial feed ratios. 15 3 M n (kda) 10 5 2 M w /M n 0 0 20 40 60 [2] 0 /[1f] 0 1 Figure S19. Plot of M n and M w /M n values of poly-f2 n as a function of the initial feed ratios of 2 to 1f. M n and M w /M n were determined by SEC with polystyrene standard (eluent = THF, temperature = 40 C). S22

Normalized intensity(a. u.) M n = 7492, PDI = 1.16 M n = 9819, PDI = 1.18 M n = 12498, PDI = 1.20 M n = 14506, PDI = 1.15 M n = 17231, PDI = 1.24 18 20 22 24 26 28 Retention time (min) Figure S20. SEC chromatograms of poly-g2 n prepared from 2 with 1g as initiator in THF at 55 C with different initial feed ratios. 15 3 M n (kda) 10 5 2 1 M w /M n 0 0 20 40 60 [2] 0 /[1g] 0 Figure S21. Plot of M n and M w /M n values of poly-g2 n as a function of the initial feed ratios of 2 to 1g. M n and M w /M n were determined by SEC with polystyrene standard (eluent = THF, temperature = 40 C). S23

Figure S22. 1 H NMR spectrum of 5a in CDCl 3 at 25 C (300 MHz). Figure S23. 1 H NMR spectrum of 5b in CDCl 3 at 25 C (600 MHz). S24

Figure S24. 1 H NMR spectrum of 5c in CDCl 3 at 25 C (600 MHz). Figure S25. 1 H NMR spectrum of 5d in CDCl 3 at 25 C (600 MHz). S25

Figure S26. 1 H NMR spectrum of 1a in CDCl 3 at 25 C (600 MHz). Figure S27. 13 C NMR spectrum of 1a in CDCl 3 at 25 C (150 MHz). S26

3000 2000 1000 Wavenumber (cm -1 ) PEt 3 Pd Cl PEt 3 Figure S28. FT-IR spectrum of 1a measured at 25 C using KBr pellets. Figure S29. 1 H NMR spectrum of 1b in CDCl 3 at 25 C (600 MHz). S27

Figure S30. 13 C NMR spectrum of 1b in CDCl 3 at 25 C (150 MHz). MeO PEt 3 Pd Cl 3000 2000 1000 Wavenumber (cm -1 ) PEt 3 Figure S31. FT-IR spectrum of 1b measured at 25 C using KBr pellets. S28

Figure S32. 1 H NMR spectrum of 1c in CDCl 3 at 25 C (600 MHz). Figure S33. 13 C NMR spectrum of 1c in CDCl 3 at 25 C (150 MHz). S29

PEt 3 Pd Cl PEt 3 3000 2000 1000 Wavenumber (cm -1 ) Figure S34. FT-IR spectrum of 1c measured at 25 C using KBr pellets. Figure S35. 1 H NMR spectrum of 1d in CDCl 3 at 25 C (600 MHz). S30

Figure S36. 13 C NMR spectrum of 1d in CDCl 3 at 25 C (150 MHz). F PEt 3 Pd Cl PEt 3 3000 2000 1000 Wavenumber (cm -1 ) Figure S37. FT-IR spectrum of 1d measured at 25 C using KBr pellets. S31

Figure S38. 1 H NMR spectrum of 1e in CDCl 3 at 25 C (600 MHz). Figure S39. 13 C NMR spectrum of 1e in CDCl 3 at 25 C (150 MHz). S32

PEt 3 Pd PEt 3 3000 2000 1000 Wavenumber (cm -1 ) Figure S40. FT-IR spectrum of 1e measured at 25 C using KBr pellets. Figure S41. 1 H NMR spectrum of 1f in CDCl 3 at 25 C (600 MHz). S33

Figure S42. 13 C NMR spectrum of 1f in CDCl 3 at 25 C (150 MHz). Figure S43. FT-IR spectrum of 1f measured at 25 C using KBr pellets. S34

Figure S44. 1 H NMR spectrum of 1g in CDCl 3 at 25 C (600 MHz). Figure S45. 13 C NMR spectrum of 1g in CDCl 3 at 25 C (150 MHz). S35

1748, C=C, Ar 1646, C=C, Ar 2098, C=C 2875, Ar-H 2969, Ar-H 2924, Ar-H 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm -1 ) Figure S46. FT-IR spectrum of 1g measured at 25 C using KBr pellets. Figure S47. 1 H NMR spectrum of 2 in CDCl 3 at 25 C (600 MHz). S36

Figure S48. 1 H NMR spectrum of 2a in CDCl 3 at 25 C (600 MHz). Figure S49. 1 H NMR spectrum of 3b in CDCl 3 at 25 C (600 MHz). S37

8 7 6 5 4 3 2 1 Figure S50. 1 H NMR spectrum of 3c in CDCl 3 at 25 C (600 MHz). Figure S51. 1 H NMR spectrum of 3d in CDCl 3 at 25 C (400 MHz). S38

Figure S52. 1 H NMR spectrum of 3e in CDCl 3 at 25 C (600 MHz). Figure S53. 1 H NMR spectrum of 3f in CDCl 3 at 25 C (600 MHz). S39

Figure S54. 1 H NMR spectrum of 4 in CDCl 3 at 25 C (600 MHz). Figure S55. 1 H NMR spectrum of poly-b3a 100 in CDCl 3 at 25 C (600 MHz). S40

Figure S56. 1 H NMR spectrum of poly-b3b 100 in CDCl 3 at 25 C (600 MHz). Figure S57. 1 H NMR spectrum of poly-b3c 100 in CDCl 3 at 25 C (600 MHz). S41

Figure S58. 1 H NMR spectrum of poly-b3d 100 in CDCl 3 at 25 C (600 MHz). Figure S59. 1 H NMR spectrum of poly-b3e 100 in CDCl 3 at 25 C (600 MHz). S42

Figure S60. 1 H NMR spectrum of poly-b4 50 in CDCl 3 at 25 C (600 MHz). Figure S61. 1 H NMR spectrum of poly-f2 30 in CDCl 3 at 25 C (600 MHz). S43

Figure S62. 1 H NMR spectrum of poly-g2 45 in CDCl 3 at 25 C (600 MHz). S44