Supporting Information for: Adi Yeori, a Israel Goldberg, a Michael Shuster, b and Moshe Kol a, *

Transcription

1 Supporting Information for: Diastereomerically-Specific Zirconium Complexes of Chiral Salan Ligands: Isospecific Polymerizations of 1-Hexene and 4-Methyl-1- pentene and Cyclopolymerization of 1,5-Hexadiene Adi Yeori, a Israel Goldberg, a Michael Shuster, b and Moshe Kol a, * a School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University, Ramat Aviv, Tel Aviv 69978, Israel. b Research and Development Group, Carmel Olefins, Ltd., Haifa 1468, Israel. S1

2 General All experiments employing metal complexes were performed under an atmosphere of dry nitrogen in a nitrogen-filled glovebox. Ether was purified by reflux and distillation under dry argon atmosphere from Na/benzophenone. Pentane was washed with HNO 3 /H 2 SO 4 prior to distillation from Na/benzophenone/tetraglyme. Toluene was refluxed over Na and distilled. 3-methylsalicylaldehyde, 3,5-di-tertbutylsalicylaldehyde, 2-(1-Adamantyl)-4-Methylphenol, trans-1,2- diaminocyclohexane, rac-trans-n,n -Dimethylcyclohexane-1,2-diamine, formaldehyde, and sodium borohydride were purchased from Aldrich Inc and used as received. ZrBn 4 was synthesized according to a known procedure. 1 NMR data for the metal complexes were recorded on a Bruker AC-200 and AC-400 spectrometers and referenced to protio impurities in benzene-d 6 (δ 7.15) and to 13 C chemical shift of benzene (δ ). NMR data for the poly(1-hexene) samples in CDCl 3 were recorded on a Bruker AC-400 spectrometer and referenced to protio impurities in the solvent (δ 77.16). NMR data for the poly(methylene-1,3-cyclopentane) samples in tetrachloroethane-d 2 were recorded on a Bruker AC-400 spectrometer and referenced to protio impurities in the solvent (δ 74.12) in 380 K. Poly(1-hexene) and atactic poly(4-methyl-1-pentene) molecular weights were detrmined by gel permeation chromatography (GPC) using TSKgel GMHHR-M column on Jasco instrument equipped with a refractive index detector. Molecular weight determination was carried out relative to polystyrene standarts using tetrahydrofuran (HPLC grade, distilled and filtered under vaccum prior to use) as the eluting solvent. High temperature GPC measurements for polymer samples insoluble at room temperature were performed in the laboratory of Prof. Moris S. Eisen in the Technion, Haifa employing the Alliance GPC-2000 high temperature GPC device. The mobile phase was 1,2,4-trichlorobenzene (HPLC grade, J. T. Baker Ltd) at 150 ºC. TCB was filtered via 0.2 µ fiberglass filter (PALL Corp.). The GPC device is equipped with 3 Styragel HT columns (Waters Corp.) and a guard column. All columns are placed in the oven and heated to 150 ºC. The RI detector at 150 ºC is used for MW determination by relative method. The data processing was done using the Millennium ver. 4.2 Software (Waters Corp.) X-ray diffraction measurements were performed on a Nonius Kappa CCD diffractometer system, using MoKα (λ= S2

3 Å) radiation. The analyzed crystals were embedded within a drop of viscous oil and freeze-cooled to ca. 110 K. The structures were solved by a combination of direct methods and Fourier techniques using SIR-97 software 2, and were refined by fullmatrix least squares with SHELXL Elemental analyses were performed in the microanalytical laboratory in the Hebrew University of Jerusalem. Ligand precursors Lig 1,2 H 2 and Lig 4 H 2 were synthesized as previously described. 4,5 The thermal behavior of poly(4-methylpentene) and poly(methylene-1,3-cyclopentane) samples was studied using a Perkin-Elmer Differential Scanning Calorimeter DSC-7 operating under N 2 atmosphere. The following procedure was employed in the case of isotactic poly(4-methylpentene): a sample of ca. 4 mg was first heated at a rate of 10 /min from 70 up to 240 C. It was kept at this temperature for 1 minute to eliminate thermal history, then cooled at the same rate down to 70 C, kept at this temperature for 1 min and repeatedly heated at a rate of 10 /min up to 240 C. Samples of poly(methylene-1,3-cyclopentane) derived from (R,R)-Lig 2 ZrBn 2 and (R,R)- Lig 3 ZrBn 2 showing melting-crystallization thermal effects were tested in a similar manner in the temperature range C. Other poly(methylene-1,3-cyclopentane) samples were tested at a rate of 20 /min in the temperature range C. A poly(methylene-1,3-cyclopentane) sample derived from rac-lig 5 ZrBn 2 was also tested at the temperature range from 100 to 450 C to detect possible thermal effects. In addition, low temperature DSC experiments for the poly(methylene-1,3- cyclopentane) samples were performed using a Setaram 131 DSC instrument under N 2 atmosphere. A sample of ca. 20 mg was first heated up to 200 C and kept at this temperature for 3 min to eliminate thermal history. Then the sample was cooled at a rate of 30 /min down to 40 C. After thermal stabilization at this temperature for ~13 min the sample was heated at a rate of 20 /min up to 100 C. The second heating run was examined aiming at detection of a glass transition. The glass transition range was characterized by the extrapolated beginning, T 1, and the extrapolated end, T 2. T g was specified as a temperature of half-vitrification. 6 S3

4 Synthesis of Lig 3,4 H 2 employing the condensation reduction methylation route: Rac Lig 3 H 2 To a stirred solution of 3-methylsalicylaldehyde (0.69 g, 5.0 mmol) in toluene (20 ml), was added dropwise trans-1,2-diaminocyclohexane (0.29 g, 2.5 mmol), and the reaction mixture was stirred and refluxed for 2 h. Upon cooling, a yellow solid has formed. The solid was isolated by vacuum filtration, and washed several times with toluene, yielding the corresponding Schiff base (Salen) intermediate (0.99 g, 100% yield). The Salen was dissolved in methanol, and 5 equiv of NaBH 4 (0.53 g, 14.1 mmol) were added portionwise with stirring. The reaction mixture was stirred overnight at RT, during which time its color turned white. The reaction mixture was poured into 100 ml of water, and the Salan[N-H] product was isolated by vacuum filtration (0.89 g, 89% yield) and obtained as white powder. To a solution of Salan[N- H] (0.32 g, 0.90 mmol) in acetonitrile (23 ml) and acetic acid (3 ml) was added formaldehyde (0.70 ml, 9.3 mmol, 37% in water), and the mixture was stirred for 20 min. Then, NaBH 4 was added (0.17 g, 4.49 mmol), and the mixture was stirred at RT overnight. Acetonitrile was removed under reduced pressure, and the residue was hydrolyzed with 2 N NaOH. The aqueous phase was extracted with dichloromethane and dried, and the solvents were removed under reduced pressure to yield Lig 3 H 2 as a cream powder (0.30 g, 89 % yield). (R,R) Lig 3 H 2 A solution of (R,R)-1,2-diammoniumcyclohexane mono-(+)-tartrate (4.8 g, 18 mmol), 7 potassium carbonate (5.0 g, 36 mmol), and water (24 ml) was stirred until complete dissolution of the salt, and then ethanol was added (96 ml). The mixture was refluxed and a solution of 3-methylsalicylaldehyde (4.9 g, 36 mmol) in 40 ml of ethanol was added dropwise over 30 min. The reflux was continued for another 2 h. Water (24 ml) was added and the stirred reaction mixture was cooled to 5ºC over 2 h and maintained at that temperature overnight. The yellow solid was collected by vacuum filtration and washed with ethanol. The solid was air dried, and was dissolved in 80 ml of dichloromethane. The organic solution was washed twice with 50 ml of water and 50 ml of saturated aqueous sodium chloride. The organic layer was dried over sodium sulfate and filtered. The solvent was removed under reduced pressure to yield the Salen intermediate (4.9 g, 79% yield). The reduction and methylation of the S4

5 intermediate was conducted as described above to yield the enantiomerically pure Salan ligand, Lig 3 H 2 (1.13 g, 80 % yield in respect to the Salan[N-H] intermediate). 1 H NMR (400 MHz, CDCl 3 ), δ 7.05 (d, J= 7.6 Hz, 2H), 7.83 (d, J= 7.3 Hz, 2H), 6.91 (t, J= 7.4 Hz, 2H), 3.80 (d, J= 13.2 Hz, 2H, AB system), 3.62 (d, J= 13.0 Hz, 2H, AB system), 2.69 (m, 2H), 2.19 (s, 3H), 2.17 (s, 3H), 2.01 (m, 2H), 1.82 (m, 2H), 1.16 (m, 4H); 13 C NMR (50.38 MHz, CDCl 3 ), δ (2C), 130.2, (4C, CH), 125.6, (4C), (2C, CH), 61.8 (2C, CH), 57.1, 25.4, 22.5 (6C, CH 2 ), 35.5, 15.9 (4C, CH 3 ). Anal. Calcd. for C 24 H 34 O 2 N 2 1/2H 2 O: C, 73.62; H, 9.01; N, Found: C, 73.62; H, 8.74; N, 6.88; [α] D = 27º, (33.4 mg/10 ml of CH 2 Cl 2, d=1/2). (R,R) Lig 4 H 2 (R,R)-Lig 4 H 2 was prepared as white powder (0.58 g, 94 %) by the same procedure described for (R,R)-Lig 3 H 2 using 3,5-di-tert-butylsalicylaldehyde as starting material. The spectroscopic data were identified to those described for the racemic ligand. 5 [α] D = 68º, (29.5 mg/10 ml of CH 2 Cl 2, d=1). Synthesis of Lig 5 H 2 employing the Mannich route: Rac Lig 5 H 2 A solution of 2-(1-Adamantyl)-4-Methylphenol (0.5 g, 2.06 mmol), rac-trans- N,N -Dimethylcyclohexane-1,2-diamine (0.14 g, 1.03 mmol) and 37% aqueous formaldehyde (10 equiv) in methanol (30 ml) was stirred and refluxed for 5 h. The mixture was cooled to room temperature and the white precipitate filtered and washed with methanol, yielding the ligand precursor Lig 5 H 2 (128 mg, 20 %). 1 H NMR (400 MHz, CDCl 3 ), δ 6.91 (d, J= 1.6 Hz, 2H), 6.62 (d, J= 1.7 Hz, 2H), 3.81 (d, J= 13.2 Hz, 2H, AB system), 3.67 (m, 2H), 2.66 (m, 2H), 2.22 (s, 6H), 2.21 (s, 6H), 2.10 (s, 12H), 1.97 (s, 6H), 1.76 (m, 2H), 1.70 (s, 12H), 1.54 (m, 4H), 1.13 (m, 2H); 13 C NMR (50.38 MHz, CDCl 3 ), δ 154.9, (4C, C), (2C, CH), (2C, C), (2C, CH), (2C, C), 61.2 (2C, CH 2 ), 57.9 (2C, CH), 40.5, 37.4 (12C, CH 2 ), 36.8 (6C, CH), 35.6 (2C, C), 29.4 (2C, CH 3 ), 25.4, 22.7 (4C, CH 2 ), 21.0 (2C, CH 3 ). Anal. Calcd. for C 44 H 62 O 2 N 2 : C, 81.18; H, 9.60; N, Found: C, 80.99; H, 9.54; N, S5

6 Synthesis of the complexes Lig 1-5 ZrBn 2 route: Synthesis of Lig 1 ZrBn 2 Lig 1 H 2 (56 mg, 0.11 mmol) was dissolved in ca. 2 ml of toluene and added dropwise to a bright yellow solution of ZrBn 4 (52 mg, 0.11 mmol) in toluene. The solution was stirred at RT for 2 h. The solution was filtered and the solvent was removed under vacuum, and the resulting yellow solid was washed with pentane (ca. 2 ml). The final yield was 96% (83 mg). The (R,R) complex was obtained analogously in 85% yield using 28 mg (0.06 mmol) of (R,R)-Lig 1 H 2. 1 H NMR (400 MHz, C 6 D 6 ), δ 7.31 (d, J=2.5 Hz, 2H), 7.22 (d, J=7.4 Hz, 4H), 7.12 (t, J= 7.8 Hz, 4H), 6.87 (t, J= 7.3 Hz, 2H), 6.53 (d, J= 2.5 Hz, 2H), 3.64 (d, J= 14.2 Hz, 2H, AB system), 2.52 (d, J= 9.8 Hz, 2H, AB system), 2.38 (d, J= 14.2 Hz, 2H, AB system), 2.21 (d, J= 9.8 Hz, 2H, AB system), 2.00 (m, 2H), 1.72 (s, 6H), 0.91 (m, 2H), 0.83 (m, 2H), 0.05 (m, 4H); 13 C NMR ( MHz, C 6 D 6 ), δ 155.0, (4C, C), 130.1, 129.3, 129.0, (8C, CH), 123.9, (4C, C), (2C, CH), 66.4 (2C, CH 2 ), 58.3 (2C, CH), 57.6 (2C, CH 2 ), 37.8 (2C, CH 3 ), 23.7, 21.1 (4C, CH 2 ). [α] D = 10.9º, (20.2 mg/5 ml of CH 2 Cl 2, d=1). Synthesis of Lig 2 ZrBn 2 Lig 2 ZrBn 2 was obtained by the same procedure employed for making Lig 1 ZrBn 2. rac- Lig 2 ZrBn 2 yield 95%. (R,R)- Lig 2 ZrBn 2 yield 97%. 1 H NMR (400 MHz, C 6 D 6 ), δ 7.64 (d, J=2.2 Hz, 2H), 7.23 (d, J=7.4 Hz, 4H), 7.12 (t, J= 7.6 Hz, 4H), 6.88 (t, J= 7.3 Hz, 2H), 6.69 (d, J= 2.3 Hz, 2H), 3.61 (d, J= 14.1 Hz, 2H, AB system), 2.57 (d, J= 9.7 Hz, 2H, AB system), 2.35 (d, J= 14.2 Hz, 2H, AB system), 2.14 (d, J= 9.8 Hz, 2H, AB system), 1.91 (m, 2H), 1.75 (s, 6H), 1.21 (m, 2H), 0.84 (m, 2H), 0.01 (m, 4H); 13 C NMR ( MHz, C 6 D 6 ), δ 156.4, (4C, C), 135.5, 131.4, 129.3, 129.1, (10C, CH), 114.0, (4C, C), 65.9 (2C, CH 2 ), 58.3 (2C, CH), 57.6 (2C, CH 2 ), 37.8 (2C, CH 3 ), 23.6, 21.0 (4C, CH 2 ). [α] D = 24.8º, (31.0 mg/5 ml of CH 2 Cl 2, d=1). Synthesis of Lig 3 ZrBn 2 Lig 3 ZrBn 2 was obtained by the same procedure employed for making Lig 1 ZrBn 2. rac- Lig 3 ZrBn 2 yield 99%. (R,R)- Lig 3 ZrBn 2 yield 83%. 1 H NMR (400 S6

7 MHz, C 6 D 6 ), δ (m, 10H), 6.87 (t, J= 7.1 Hz, 2H), 6.72 (t, J= 7.4 Hz, 2H), 6.61 (d, J= 6.2 Hz, 2H), 3.96 (d, J= 13.8 Hz, 2H, AB system), 2.66 (d, J= 13.8 Hz, 2H, AB system), 2.58 (d, J= 10.0 Hz, 2H, AB system), 2.48 (d, J= 10.0 Hz, 2H, AB system), 2.45 (s, 6H), 2.20 (m, 2H), 1.75 (s, 6H), 1.05 (m, 2H), 0.99 (m, 2H), 0.16 (m, 4H); 13 C NMR ( MHz, C 6 D 6 ), δ 159.1, (4C, C), 131.5, 128.9, 128.0, (8C, CH), 126.6, (4C, C), 121.9, (4C, CH), 66.9, 58.5 (4C, CH 2 ), 57.8 (2C, CH), 37.6 (2C, CH 3 ), 24.0, 21.2 (4C, CH 2 ), 17.1 (2C, CH 3 ). Crystal data for rac-lig 3 ZrBn 2 : C 45 H 54 N 2 O 2 Zr (with 1 molecule of toluene); M = ; monoclinic; space group C C ; a = (2), b = (2), c = (2) Å; V = (9) Å 3 ; T = 110(2) K; Z = 4; D c = g cm -3 ; µ (Mo Kα) = mm -1 ; R 1 = and wr 2 = for 6988 reflections with I > 2σ(I); R 1 = , wr 2 = for all 7762 unique reflections. [α] D = 81.4º, (16.4 mg/5 ml of CH 2 Cl 2, d=1). Synthesis of Lig 4 ZrBn 2 (R,R)- Lig 4 ZrBn 2 was obtained by the same procedure employed for making Lig 1 ZrBn 2 in 95% yield. 1 H NMR (400 MHz, C 6 D 6 ), δ 7.60 (d, J=2.4 Hz, 2H), 7.24 (d, J=7.3 Hz, 4H), 7.06 (t, J= 7.8 Hz, 4H), 6.76 (t, J= 7.3 Hz, 2H), 6.73 (d, J= 2.4 Hz, 2H), 3.75 (d, J= 13.6 Hz, 2H, AB system), 3.05 (d, J= 10.5 Hz, 2H, AB system), 2.64 (d, J= 11.1 Hz, 4H, AB system), 2.08 (m, 2H), 1.84 (s, 6H), 1.32 (s, 18H), 1.31 (s, 18H), 1.15 (m, 2H), 0.34 (m, 6H); 13 C NMR ( MHz, C 6 D 6 ), δ 157.7, 149.8, 141.1, (8C, C), 128.6, (4C, CH), (2C, C), 124.9, 124.4, (6C, CH), 70.8, 59.1 (4C, CH 2 ), 57.6 (2C, CH), 38.9 (2C, CH 3 ), 35.6, 34.4 (4C, C), 31.9, 30.7 (12C, CH 3 ), 24.1, 21.2 (4C, CH 2 ). [α] D = 74.0º, (10.3 mg/3 ml of CH 2 Cl 2, d=1). Synthesis of rac-lig 5 ZrBn 2 Lig 5 ZrBn 2 was obtained by the same procedure employed for making Lig 1 ZrBn 2 (87% yield). 1 H NMR (400 MHz, C 6 D 6 ), δ 7.26 (d, J=7.4 Hz, 4H), 7.21 (d, J=1.4 Hz, 2H), 7.11 (t, J= 7.6 Hz, 4H), 6.77 (t, J= 7.3 Hz, 2H), 6.45 (d, J= 1.3 Hz, 2H), 3.73 (d, J= 13.6 Hz, 2H, AB system), 3.23 (d, J= 10.5 Hz, 2H, AB system), 2.78 (d, J= 10.5 Hz, 2H, AB system), 2.65 (d, J= 13.6 Hz, 2H, AB system), 2.54 (m, 12H), 2.36 (m, 2H), 2.29 (s, 6H), 2.22 (s, 6H), 2.13 (m, 6H), 1.92 (s, 6H), 1.90 (m, 6H), 1.15 (m, 2H), 1.01 (m, 2H), 0.22 (m, 4H); 13 C NMR ( MHz, C 6 D 6 ), δ 158.0, 150.2, (6C, C), 128.8, 128.6, 128.5, (8C, CH), (2C, C), (4C, CH), S7

8 72.1, 58.7 (4C, CH 2 ), 57.7 (2C, CH), 41.5 (6C, CH 2 ), 38.8 (6C, CH), 37.6 (6C, CH 2 ), 29.8 (2C, CH 3 ), 23.9, 21.4 (4C, CH 2 ), 21.1 (2C, CH 3 ). Crystal data for rac-lig 5 ZrBn 2 : C 70 H 98 N 2 O 5 Zr (with 3 molecules of THF); M = ; monoclinic; space group P2 1 /c; a = (8), b = (16), c = (13) Å; V = (7) Å 3 ; T = 110(2) K; Z = 4; D c = g cm -3 ; µ (Mo Kα) = mm -1 ; R 1 = and wr 2 = for 4413 reflections with I > 2σ(I); R 1 = , wr 2 = for all unique reflections. General procedure for the polymerization of neat 1-hexene B(C 6 F 5 ) 3 (1-2 equiv) was dissolved in ca. 1 ml of 1-hexene and added to a stirred solution of the corresponding Lig X ZrBn 2 (11 µmol) in 1-hexene at room temperature. The resulting mixture was stirred until 1-hexene had started to boil and the resulting polymer had become viscous (X = 1,2,3), or after a given time (X = 4,5). The remaining olefin was evaporated under vacuum yielding poly(1-hexene) as an orangebrown sticky oil (see table 1). Table 1: 1-Hexene Polymerization Data for Lig 1-5 ZrBn 2 No. Cat. 1-Hexene Polymerization Polymer Activity Mw PDI (g) Time (min) Obtained (g) (g polymer mmol -1 cat h -1 ) (g/mol) 1 (R,R) , Lig 1 ZrBn 2 2 (R,R) - Lig 2 ZrBn 2 3 Rac Lig 3 ZrBn 2 4 (R,R) Lig 4 ZrBn 2 5 (R,R) , , mg low 21, mg low 26, Lig 4 ZrBn 2 6 Rac low 47, Lig 5 ZrBn 2 S8

9 ppm Figure 1: Atactic poly(1-hexene) produced from (R,R)-Lig 1 ZrBn ppm Figure 2: Isotactic poly(1-hexene) produced from (R,R)-Lig 4 ZrBn p p m Figure 3: Isotactic poly(1-hexene) produced from rac-lig 5 ZrBn 2 S9

10 General procedure for the polymerization of 4-methyl-1-pentene B(C 6 F 5 ) 3 (1-2 eq.) was dissolved in ca. 1 ml of 4-methyl-1-pentene and added to a stirred solution of the Lig X ZrBn 2 (11 µmol) in 4-methyl-1-pentene at room temperature. The resulting mixture was stirred until 4-methyl-1-pentene had started to boil and the resulting polymer became viscous (X = 1,2,3,5), or after a given time (X = 4). The remaining olefin was removed under vacuum yielding poly(4-methyl-1- pentene) as a yellow-white solid (see table 2). Table 2: 4-methyl-1-pentene (4-MP) Polymerization Data for Lig 1-5 ZrBn 2 No. Cat. 4-MP Polymerization Polymer Activity Mw PDI (g) Time (min) Obtained (g) (g polymer mmol -1 cat h -1 ) (g/mol) 1 (R,R) , Lig 1 ZrBn 2 2 (R,R) - Lig 2 ZrBn 2 3 (R,R) - Lig 3 ZrBn 2 4 (R,R) , , mg Very low 15, Lig 4 ZrBn 2 5 Rac mg low 24, Lig 5 ZrBn 2 (60 % fraction) 5, (40 % fraction) ppm Figure 4: Atactic poly(4-methyl-1-pentene) produced from (R,R)-Lig 2 ZrBn 2 S10

11 ppm Figure 5: Isotactic poly(4-methyl-1-pentene) produced from (R,R)-Lig 4 ZrBn 2 Figure 6: DSC first heating thermograms of poly(4-methyl-1-pentene) produced from rac-lig 5 ZrBn 2 (top), rac-lig 4 ZrBn 2 (middle) and (R,R)-Lig 4 ZrBn 2 (bottom). Figure 7: DSC cooling thermograms of poly(4-methyl-1-pentene) produced from rac- Lig 5 ZrBn 2 (top), rac-lig 4 ZrBn 2 (middle) and (R,R)-Lig 4 ZrBn 2 (bottom). S11

12 Figure 8: DSC second heating thermograms of poly(4-methyl-1-pentene) produced from rac-lig 5 ZrBn 2 (top), rac-lig 4 ZrBn 2 (middle) and (R,R)-Lig 4 ZrBn 2 (bottom). General procedure for the polymerization of neat 1,5-hexadiene B(C 6 F 5 ) 3 (1-2 equiv) was dissolved in ca. 1 ml of 1,5-hexadiene and added to a stirred solution of the Lig X ZrBn 2 (11 µmol) in 1,5-hexadiene at room temperature. The resulting mixture was stirred until 1,5-hexadiene was started to boil and the resulting polymer became viscous (X= 1,2,3,5), or after a given time (X=4). The remaining olefin was removed under vacuum yielding poly(methylene-1,3- cyclopentane) as a yellow-white solid (see table 3). General procedure for the polymerization of 1,5-hexadiene in solution B(C 6 F 5 ) 3 (1-2 equiv) was dissolved in ca. 1 ml of a mixture of 1,5-hexadiene in toluene or heptane ( ml) and added to a stirred solution of the Lig X ZrBn 2 (11 µmol) in 1,5-hexadiene at room temperature. The resulting mixture was stirred until the resulting mixture started to be hot and viscous (X= 1,2,3), or after a given time (X= 4). The remaining solution was evaporated under vacuum yielding poly(methylene-1,3-cyclopentane) as a yellow-white solid (see table 3). S12

13 Table 3: 1,5-hexadiene (1,5-HD) Polymerization Data for Lig 1-5 ZrBn 2 No. Cat. 1,5-HD solvent Polymerization Polymer Activity (g) Time (min) Obtained (g) (g polymer mmol -1 cat h -1 ) 1 (R,R) neat Lig 1 ZrBn 2 2 (R,R) - Lig 1 ZrBn 2 3 (R,R) - Lig 1 ZrBn 2 4 (R,R) Lig 2 ZrBn 2 5 (R,R) Lig 2 ZrBn 2 6 rac Lig 3 ZrBn 2 7 rac Lig 3 ZrBn 2 8 (R,R) Lig 3 ZrBn 2 9 (R,R) Lig 4 ZrBn 2 10 (R,R) Lig 4 ZrBn 2 11 rac Lig 4 ZrBn 2 12 (R,R) Lig 4 ZrBn 2 13 rac 2.7 Toluene 1 ml Heptane ml 0.2 Toluene eq 1.5 ml 0.4 Toluene eq 2.5 ml 2.3 neat Toluene eq 1.5 ml 0.3 Toluene eq 1.5 ml 2.2 neat low 2.0 neat Over night low 1.7 neat Over night low 0.8 Heptane Over night low 2 ml 1.1 neat Lig 5 ZrBn 2 S13

14 ppm Figure 9: Poly(methylene-1,3-cyclopentane) produced from (R,R)-Lig 2 ZrBn 2. (A) experimental Integration ratio: 4:9.1:19.5 : 1:4:5.8 (9.3 : 20.9 : 44.9 : 2.3 : 9.3 : 13.3) (B) simulated Figure 10: poly(methylene-1,3-cyclopentane) produced from (R,R)-Lig 2 ZrBn 2, actual (A) and simulated (B; σ = 0.25, α = 0.75) 13 C NMR spectra for C 4,5. S14

15 Figure 11: DSC thermograms of poly(methylene-1,3-cyclopentane) produced from (R,R)-Lig 1 ZrBn 2. Figure 12: DSC thermograms of poly(methylene-1,3-cyclopentane) produced from (R,R)-Lig 2 ZrBn 2. Figure 13: DSC thermograms of poly(methylene-1,3-cyclopentane) produced from (R,R)-Lig 3 ZrBn 2. S15

16 Figure 14: DSC thermograms of poly(methylene-1,3-cyclopentane) produced from rac-lig 4 ZrBn 2. Figure 15: DSC thermograms of poly(methylene-1,3-cyclopentane) produced from (R,R)-Lig 4 ZrBn 2. Figure 16: DSC thermograms of poly(methylene-1,3-cyclopentane) produced from rac-lig 5 ZrBn 2 in the temperature range C S16

17 5 0-5 heat flow T1=8 Tg~12 T2= temperature, C Figure 17: Low Temp DSC thermogram of poly(methylene-1,3-cyclopentane) produced from rac-lig 1 ZrBn heat flow T g=9 T 1=4 T 2= temperature, C Figure 18: Low Temp DSC thermogram of poly(methylene-1,3-cyclopentane) produced from rac-lig 2 ZrBn 2. S17

18 5 0-5 heat flow T 1=-1 T g ~5 T 2= temperature, C Figure 19: Low Temp DSC thermogram of poly(methylene-1,3-cyclopentane) produced from rac-lig 3 ZrBn Heat flow T 1=-6 T g~-3.5 T 2= Temperature, C Figure 20: Low Temp DSC thermogram of poly(methylene-1,3-cyclopentane) produced from rac-lig 4 ZrBn 2. S18

19 Heat flow -15 T 1=-6 T g~-4 T 2= Temperature, C Figure 21: Low Temp DSC thermogram of poly(methylene-1,3-cyclopentane) produced from rac-lig 5 ZrBn 2. References (1) Zucchini, U.; Alizzati, E.; Giannini, U. J. Organomet. Chem. 1971, 26, 357. (2) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.; Burla, M. C.; Polidori, G.; Camali, M. J. Appl. Cryst. 1994, 27, 435. (3) Sheldrick, G. M. SHELXL-97 Program; University of Göttingen, Germany, (4) Yeori, A.; Groysman, S.; Goldberg, I.; Kol, M. Inorg. Chem. 2005, 44, (5) Balsells, J.; Carroll, P. J.; Walsh, P. J. Inorg. Chem. 2001, 40, (6) Wunderlich, B. Thermal Analysis of Polymeric Materials. Springer-Verlag, 2005, p.179. (7) Larrow, J. F.; Jacobsen, E. N. Org. Synth. 1997, 75, 1. S19