Chiral Sila[1]ferrocenophanes

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Supporting Information Thermal Ring-Opening Polymerization of Planar- Chiral Sila[1]ferrocenophanes Elaheh Khozeimeh Sarbisheh, Jose Esteban Flores, Brady Anderson, Jianfeng Zhu, # and Jens Müller*, Department of Chemistry and # Saskatchewan Structural Sciences Centre, University of Saskatchewan, 110 Science Place, Saskatoon, Saskatchewan S7N 5C9, Canada. Table of Contents Synthesis of R-1, R,S p -2, and rac-5 S2 References S3 Figure S1. Molecular structure of rac-5 with thermal ellipsoids at 50% probability level. S4 Table S1. Crystal and Structural Refinement Data for Compound rac-4 and rac-5. S4 Table S2. Bond Lengths [Å] and Angles [deg] for rac-4. S5 Table S3. Bond Lengths [Å] and Angles [deg] for rac-5. S6 Figure S2. 1 H NMR spectrum of (R,S p )-2-[1-(acetoxy)ethyl]-1,1'-dibromoferrocene S7 Figure S3. 1 H NMR spectrum of S p -3 S8 Figure S4. 13 C NMR spectrum of S p -3 S9 Figure S5. 1 H NMR spectrum of S p -4 S10 Figure S6. 13 C NMR spectrum of S p -4 S11 Figure S7. 29 Si NMR spectrum of S p -4 S12 Figure S8. 1 H NMR spectrum of rac-4 S13 Figure S9. 13 C NMR spectrum of rac-4 S14 Figure S10. 1 H NMR spectrum of rac-5 S15 Figure S11. 13 C NMR spectrum of rac-5 S16 Figure S12. 29 Si NMR spectrum of rac-5 S17 Figure S13. 1 H NMR spectrum of (S p -4) n S18 Figure S14. 13 C NMR spectrum of (S p -4) n S19 Figure S15. 29 Si NMR spectrum of (S p -4) n S20 Figure S16. 1 H NMR spectrum of (rac-4) n S21 Figure S17. 13 C NMR spectrum of (rac-4) n S22 Figure S18. 29 Si NMR spectrum of (rac-4) n S23 Figure S19. Differential scanning calorimetry (DSC) thermogram of rac-4 S24 Figure S20. Differential scanning calorimetry (DSC) thermogram of S p,s p -4 S25 Figure S21. GPC traces of polymer (rac-4) n S26 Figure S22. GPC traces of polymer (S p -4) n S27 Figure S23. Illustration of a statistical distribution for the different environments in (rac-4) n S28 S1

Synthesis of (R)-1-[1-(dimethylamino)ethyl]ferrocene (R-1) (based on the procedure described in reference 1). Species (R)-1-[1-(acetoxy)ethyl]ferrocene 1 (7.02 g, 25.8 mmol) was dissolved in thf (235 ml). Dimethylamine (190.0 ml, 1.5 mol, 40% solution in water) was added, and the reaction mixture was stirred overnight at r.t. The reaction mixture was poured in saturated NH4Cl solution (300 ml). From this point on the manipulation was done under air. The phases were separated and the aqueous phase was extracted with Et2O (3 120 ml). The organic layers were washed with water and brine. The combined organic layers were dried over anhydrous Na2SO4, filtered, and concentrated using a rotatory evaporator. The crude product was purified by flash column chromatography (silica gel; hexanes/et2o, 1 : 1 plus 5% NEt3) and afforded the amine R-1 as a red oil (5.72 g, 86%). NMR data was consistent with literature data. 1 Synthesis of (R,S p )-2-[1-(dimethylamino)ethyl]-1,1'-dibromoferrocene (R,S p -2) (based on the procedure described in references 2 and 3). To a stirred solution of R-1 1 (2.31 g, 8.99 mmol) in Et2O (18 ml), nbuli (2.5 M in hexanes, 18.0 ml, 45 mmol) was added dropwise over 15 min at r.t., followed by the dropwise addition of tetramethylethylendiamine (tmeda) (3.40 ml, 22.7 mmol) over 10 min at r.t. After several minutes, the color of the mixture changed from orange to red. More Et2O (51 ml) was added and the reaction mixture was stirred overnight (16 h) at r.t. More Et2O (60 ml) was added, before the reaction mixture was cooled down to -78 C. A cold solution (-78 C) of 1,2- dibromotetrachloroethane (16.13 g, 49.53 mmol) in thf (165 ml) was added dropwise via cannula over 30 min to this mixture. The resulting yellow suspension was stirred another 1 h at -78 C and 2 h at r.t. The reaction mixture was quenched with saturated aqueous Na2S2O3 solution at 0 C. From this point on the manipulation was done under air. The phases were separated and the aqueous phase was extracted with Et2O (3 100 ml). The combined organic phases were poured into a saturated aqueous NH4Cl solution (300 ml). The aqueous phase was separated, neutralized with dropwise addition of 1 M KOH solution, and extracted with Et2O (250 ml). After being washed with water (100 ml) and brine (250 ml), the combined organic layers were dried over anhydrous Na2SO4, filtered, and concentrated using a rotatory evaporator. The crude product was purified by flash column chromatography (silica gel; hexanes/etoac, 2 : 1 plus 5% Et3N) and afforded R,Sp-2 as an orange oil (2.82 g, 76%). Note: compound R,Sp-2 contains ca. 12% of (R,Sp)-2-[1-(dimethylamino)ethyl]-1-bromoferrocene as an impurity. NMR data was consistent with literature. 3 Preparation of sila[1]ferrocenophane rac-5. Species rac-3 (0.40 g, 1.0 mmol) was dissolved in a mixture of thf (0.94 ml) and hexanes (8.4 ml) and cooled to 0 C. A solution of nbuli (2.5 M in hexanes, 0.88 ml, 2.2 mmol) was added dropwise and the reaction mixture was stirred at 0 C for 30 min. Et2SiCl2 (0.16 ml, 1.1 mmol) was added dropwise via syringe within 1 min at 0 C and the color of the solution changed from orange to red, along with formation of a white precipitate. After stirring of the reaction mixture for 15 min at 0 C, all volatiles were removed under vacuum and the resulting red residue was dissolved in hexanes (10 ml). Solids were removed by filtration and solvents were removed under vacuum. The crude material was purified by flash column chromatography (neutral alumina; hexanes/et3n, 10 : 1) and crystallization in hexanes (3 ml) at -80 C resulted in rac-5 as red crystals (0.24 g, 75%). 1 H NMR (C6D6, 600.2 MHz): δ = 0.92 [two overlapping quartets, 2H, J = 8.0 Hz, Si(CH2CH3)2], 1.08 [m, 2H, Si(CH2CH3)2 overlaps with doublet at 1.10], 1.10 [d, 3H, J = 7.0 Hz, CH(CH3)2], 1.16 [t, 3H, J = 8.0 Hz, Si(CH2CH3)2; overlaps with triplet at 1.19], 1.19 [t, 3H, J = 8.0 Hz, Si(CH2CH3)2; overlaps with triplet at 1.16 and doublet at 1.19], 1.19 [d, 3H, J = 7.0 S2

Hz, CH(CH3)2], 2.60 [sept, 1H, J = 7.0 Hz, CH(CH3)2], 3.65 (m, 1H, Cp), 3.86 (m, 1H, Cp), 3.93 (m, 1H, Cp), 4.33 (m, 1H, Cp), 4.36 (m, 1H, Cp), 4.40 (m, 1H, Cp), 4.52 (m, 1H, Cp) ppm; 13 C{ 1 H} NMR (C6D6, 150.9 MHz): = 3.1 (Si(CH2CH3)2), 5.1 (Si(CH2CH3)2), 6.5 (Si(CH2CH3)2), 6.6 (Si(CH2CH3)2), 21.5 (CH(CH3)2), 27.8 (CH(CH3)2), 29.3 (CH(CH3)2), 30.4 (ipso-cp Si ), 33.2 (ipso-cp Si ), 74.0 (CH of Cp), 75.2 (CH of Cp), 75.8 (CH of Cp), 76.3 (CH of Cp), 76.6 (CH of Cp), 77.8 (CH of Cp), 80.8 (CH of Cp), 105.6 (ipso-cp ipr ) ppm; 29 Si NMR (C6D6, 119.2 MHz): δ = 1.1 ppm. HRMS (FDI; m/z): [M + ] calcd for 12 C17 1 H24 56 28 Si, 312.0997; found, 312.1010. Elemental Anal. Calcd. for C17H24Si (312.31): C, 65.38; H, 7.75. Found: C, 65.24; H, 6.98. References (1) Tappe, K.; Knochel, P. Tetrahedron-Asymmetry 2004, 15, 91-102. (2) ng, X.; Pugin, B.; Küsters, E.; Sedelmeier, G.; Blaser, H.-U. Adv. Syn. Catal. 2007, 349, 1803-1807. (3) Köllner, C.; Pugin, B.; Togni, A. J. Am. Chem. Soc. 1998, 120, 10274-10275. S3

Figure S1. Molecular structure of rac-5 with thermal ellipsoids at 50% probability level. Hydrogen atoms are omitted for clarity. For bond lengths [Å] and angles [deg] see Table S3. Experimental and calculated distortion angles (in degrees; B3PW91/6-311G+(d,p) values in brackets): = 19.74(12) [20.0], = 165.34(2) [165.6], / ' = 37.92(14)/38.23(13) [37.1/37.7], = 96.13(8) [95.2], = 86.29(8) [88.0] (see Figure 3 for definitions of distortion angles). Table S1. Crystal and Structural Refinement Data for Compound rac-4 and rac-5. rac-4 rac-5 empirical formula C15H20Si C17H24Si fw 284.25 312.30 cryst. size / mm 3 0.080 0.400 0.400 0.230 0.150 0.070 cryst. system, monoclinic monoclinic space group C2/c P2 1 /n Z 8 4 a / Å 18.4051(9) 13.4712(10) b / Å 14.4959(9) 7.2681(5) c / Å 13.7450(10) 16.4034(11) α / 90 90 / 131.417(2) 95.905(3) / 90 90 volume / Å 3 2750.0(3) 1597.54(19) calc / mg m -3 1.373 1.298 temperature / K 173(2) 173(2) calc./ mm -1 1.159 1.004 range / 2.04 to 28.89 2.497 to 27.497 Completeness to theta = 25.242 / % 99.9 99.9 collected reflections 15221 24981 independent reflections 3597 [R(int) = 0.0288] 3685 [R(int) = 0.0437] absorption correction multi-scan multi-scan data / restraints / params 3597 / 0 / 158 3685 / 0 / 176 goodness-of-fit 1.064 1.024 R1 [I > 2 (I)] a 0.0293 0.0326 wr2 (all data) a 0.0769 0.0788 largest diff. peak and hole, elect / e Å -3 0.610 and -0.389 0.298 and -0.291 a 2 R 1 = [ F o - F c ]/[ F o ] for [F o > 2 (F o2 )], wr 2 = {[ w(f o2 -F c2 ) 2 ]/[ w(f o2 ) 2 ]} 1/2 [all data]. S4

Table S2. Bond Lengths [Å] and Angles [deg] for rac-4. (1)-C(6) 2.0139(15) C(10)-(1)-C(3) 128.11(7) (1)-C(1) 2.0181(15) C(2)-(1)-C(3) 40.31(6) (1)-C(5) 2.0246(16) C(4)-(1)-C(3) 40.09(7) (1)-C(7) 2.0284(16) C(8)-(1)-C(3) 136.14(7) (1)-C(10) 2.0331(16) C(9)-(1)-C(3) 121.16(7) (1)-C(2) 2.0476(15) C(6)-(1)-Si(1) 44.24(5) (1)-C(4) 2.0765(16) C(1)-(1)-Si(1) 44.40(4) (1)-C(8) 2.0784(16) C(5)-(1)-Si(1) 72.18(5) (1)-C(9) 2.0851(17) C(7)-(1)-Si(1) 73.50(5) (1)-C(3) 2.0881(16) C(10)-(1)-Si(1) 73.65(5) (1)-Si(1) 2.7108(5) C(2)-(1)-Si(1) 75.35(5) Si(1)-C(15) 1.8637(17) C(4)-(1)-Si(1) 110.69(5) Si(1)-C(14) 1.8645(18) C(8)-(1)-Si(1) 111.42(5) Si(1)-C(6) 1.8926(17) C(9)-(1)-Si(1) 111.54(5) Si(1)-C(1) 1.8983(16) C(3)-(1)-Si(1) 112.35(5) C(1)-C(5) 1.458(2) C(15)-Si(1)-C(14) 110.37(8) C(1)-C(2) 1.462(2) C(15)-Si(1)-C(6) 111.74(8) C(2)-C(3) 1.425(2) C(14)-Si(1)-C(6) 111.54(8) C(2)-C(11) 1.514(2) C(15)-Si(1)-C(1) 116.45(7) C(3)-C(4) 1.427(2) C(14)-Si(1)-C(1) 110.06(8) C(3)-H(3) 1.0000 C(6)-Si(1)-C(1) 95.98(7) C(4)-C(5) 1.423(2) C(15)-Si(1)-(1) 128.17(6) C(6)-C(10) 1.450(2) C(14)-Si(1)-(1) 121.42(6) C(6)-C(7) 1.454(2) C(6)-Si(1)-(1) 47.93(5) C(7)-C(8) 1.424(2) C(1)-Si(1)-(1) 48.05(5) C(8)-C(9) 1.424(3) C(5)-C(1)-C(2) 104.93(14) C(8)-H(8) 1.0000 C(5)-C(1)-Si(1) 115.26(11) C(9)-C(10) 1.428(2) C(2)-C(1)-Si(1) 122.61(11) C(11)-C(12) 1.522(2) C(5)-C(1)-(1) 69.11(9) C(11)-C(13) 1.538(2) C(2)-C(1)-(1) 70.00(9) C(6)-(1)-C(1) 88.63(6) Si(1)-C(1)-(1) 87.55(6) C(6)-(1)-C(5) 107.99(7) C(3)-C(2)-C(1) 109.05(13) C(1)-(1)-C(5) 42.27(6) C(3)-C(2)-C(11) 125.21(14) C(6)-(1)-C(7) 42.17(7) C(1)-C(2)-C(11) 125.37(14) C(1)-(1)-C(7) 110.11(6) C(3)-C(2)-(1) 71.37(9) C(5)-(1)-C(7) 99.60(7) C(1)-C(2)-(1) 67.84(8) C(6)-(1)-C(10) 42.00(7) C(11)-C(2)-(1) 132.34(11) C(1)-(1)-C(10) 109.51(6) C(2)-C(3)-C(4) 108.48(14) C(5)-(1)-C(10) 145.81(7) C(2)-C(3)-(1) 68.32(8) C(7)-(1)-C(10) 69.13(7) C(4)-C(3)-(1) 69.52(9) C(6)-(1)-C(2) 111.73(6) C(5)-C(4)-C(3) 107.85(14) C(1)-(1)-C(2) 42.15(6) C(5)-C(4)-(1) 67.75(9) C(5)-(1)-C(2) 69.30(6) C(3)-C(4)-(1) 70.39(9) C(7)-(1)-C(2) 148.82(7) C(4)-C(5)-C(1) 109.68(14) C(10)-(1)-C(2) 103.16(6) C(4)-C(5)-(1) 71.67(10) C(6)-(1)-C(4) 147.99(7) C(1)-C(5)-(1) 68.63(8) C(1)-(1)-C(4) 70.21(6) C(10)-C(6)-C(7) 104.99(14) C(5)-(1)-C(4) 40.58(7) C(10)-C(6)-Si(1) 119.39(11) C(7)-(1)-C(4) 122.53(7) C(7)-C(6)-Si(1) 118.68(12) C(10)-(1)-C(4) 168.08(7) C(10)-C(6)-(1) 69.71(9) C(2)-(1)-C(4) 68.29(6) C(7)-C(6)-(1) 69.45(9) C(6)-(1)-C(8) 70.05(7) Si(1)-C(6)-(1) 87.83(6) C(1)-(1)-C(8) 150.47(7) C(8)-C(7)-C(6) 109.39(15) C(5)-(1)-C(8) 124.44(7) C(8)-C(7)-(1) 71.61(9) C(7)-(1)-C(8) 40.55(7) C(6)-C(7)-(1) 68.38(9) C(10)-(1)-C(8) 68.13(7) C(7)-C(8)-C(9) 108.23(16) C(2)-(1)-C(8) 165.62(7) C(7)-C(8)-(1) 67.84(9) C(4)-(1)-C(8) 118.32(7) C(9)-C(8)-(1) 70.26(9) C(6)-(1)-C(9) 70.03(7) C(8)-C(9)-C(10) 107.72(15) C(1)-(1)-C(9) 149.76(7) C(8)-C(9)-(1) 69.74(10) C(5)-(1)-C(9) 164.43(7) C(10)-C(9)-(1) 67.76(9) C(7)-(1)-C(9) 68.23(7) C(9)-C(10)-C(6) 109.65(15) C(10)-(1)-C(9) 40.55(7) C(9)-C(10)-(1) 71.68(10) C(2)-(1)-C(9) 126.13(7) C(6)-C(10)-(1) 68.29(9) C(4)-(1)-C(9) 137.66(7) C(2)-C(11)-C(12) 113.42(14) C(8)-(1)-C(9) 40.00(7) C(2)-C(11)-C(13) 108.36(13) C(6)-(1)-C(3) 152.00(6) C(12)-C(11)-C(13) 110.52(14) C(1)-(1)-C(3) 69.86(6) C(5)-(1)-C(3) 68.12(7) C(7)-(1)-C(3) 162.41(7) S5

Table S3. Bond Lengths [Å] and Angles [deg] for rac-5. (1)-C(1) 2.0097(18) (1)-C(6) 2.0111(17) (1)-C(5) 2.0219(19) (1)-C(10) 2.0242(18) (1)-C(7) 2.0326(19) (1)-C(2) 2.0359(18) (1)-C(9) 2.0713(19) (1)-C(4) 2.0729(19) (1)-C(8) 2.075(2) (1)-C(3) 2.0803(18) (1)-Si(1) 2.6995(6) Si(1)-C(14) 1.867(2) Si(1)-C(15) 1.8688(19) Si(1)-C(6) 1.8887(19) Si(1)-C(1) 1.8976(18) C(1)-C(5) 1.452(3) C(1)-C(2) 1.457(2) C(2)-C(3) 1.424(3) C(2)-C(11) 1.513(3) C(3)-C(4) 1.419(3) C(4)-C(5) 1.415(3) C(6)-C(10) 1.448(2) C(6)-C(7) 1.448(3) C(7)-C(8) 1.423(3) C(8)-C(9) 1.418(3) C(9)-C(10) 1.420(3) C(11)-C(13) 1.531(3) C(11)-C(12) 1.532(3) C(14)-C(16) 1.523(3) C(15)-C(17) 1.531(3) C(1)-(1)-C(6) 88.94(7) C(1)-(1)-C(5) 42.23(8) C(6)-(1)-C(5) 108.16(7) C(1)-(1)-C(10) 108.57(8) C(6)-(1)-C(10) 42.04(7) C(5)-(1)-C(10) 145.22(8) C(1)-(1)-C(7) 111.55(8) C(6)-(1)-C(7) 41.97(8) C(5)-(1)-C(7) 101.13(8) C(10)-(1)-C(7) 68.95(8) C(1)-(1)-C(2) 42.22(7) C(6)-(1)-C(2) 111.91(7) C(5)-(1)-C(2) 69.43(7) C(10)-(1)-C(2) 101.89(8) C(7)-(1)-C(2) 149.80(8) C(1)-(1)-C(9) 148.59(8) C(6)-(1)-C(9) 70.10(8) C(5)-(1)-C(9) 166.30(8) C(10)-(1)-C(9) 40.57(8) C(7)-(1)-C(9) 68.17(8) C(2)-(1)-C(9) 124.13(8) C(1)-(1)-C(4) 70.05(8) C(6)-(1)-C(4) 147.96(8) C(5)-(1)-C(4) 40.42(7) C(10)-(1)-C(4) 167.50(8) C(7)-(1)-C(4) 123.42(8) C(2)-(1)-C(4) 68.42(8) C(9)-(1)-C(4) 138.14(8) C(1)-(1)-C(8) 151.97(8) C(6)-(1)-C(8) 69.97(8) C(5)-(1)-C(8) 126.32(8) C(10)-(1)-C(8) 68.06(8) C(7)-(1)-C(8) 40.52(8) C(2)-(1)-C(8) 163.58(8) C(9)-(1)-C(8) 40.00(8) C(4)-(1)-C(8) 119.27(9) C(1)-(1)-C(3) 69.74(7) C(6)-(1)-C(3) 152.32(8) C(5)-(1)-C(3) 67.90(8) C(10)-(1)-C(3) 127.56(8) C(7)-(1)-C(3) 162.95(8) C(2)-(1)-C(3) 40.45(7) C(9)-(1)-C(3) 120.22(8) C(4)-(1)-C(3) 39.96(7) C(8)-(1)-C(3) 135.56(8) C(1)-(1)-Si(1) 44.60(5) C(6)-(1)-Si(1) 44.35(5) C(5)-(1)-Si(1) 72.03(6) C(10)-(1)-Si(1) 73.18(5) C(7)-(1)-Si(1) 74.07(6) C(2)-(1)-Si(1) 75.72(5) C(9)-(1)-Si(1) 111.33(6) C(4)-(1)-Si(1) 110.50(6) C(8)-(1)-Si(1) 111.80(6) C(3)-(1)-Si(1) 112.61(6) C(14)-Si(1)-C(15) 110.81(9) C(14)-Si(1)-C(6) 110.38(9) C(15)-Si(1)-C(6) 112.80(9) C(14)-Si(1)-C(1) 116.78(9) C(15)-Si(1)-C(1) 109.26(9) C(6)-Si(1)-C(1) 96.13(8) C(14)-Si(1)-(1) 127.77(6) C(15)-Si(1)-(1) 121.39(7) C(6)-Si(1)-(1) 48.10(5) C(1)-Si(1)-(1) 48.04(5) C(5)-C(1)-C(2) 105.18(15) C(5)-C(1)-Si(1) 114.64(13) C(2)-C(1)-Si(1) 122.82(13) C(5)-C(1)-(1) 69.34(10) C(2)-C(1)-(1) 69.86(10) Si(1)-C(1)-(1) 87.35(7) C(3)-C(2)-C(1) 108.57(16) C(3)-C(2)-C(11) 124.93(16) C(1)-C(2)-C(11) 126.32(16) C(3)-C(2)-(1) 71.46(11) C(1)-C(2)-(1) 67.93(10) C(11)-C(2)-(1) 130.34(13) C(4)-C(3)-C(2) 108.74(16) C(4)-C(3)-(1) 69.74(10) C(2)-C(3)-(1) 68.10(10) C(5)-C(4)-C(3) 107.88(17) C(5)-C(4)-(1) 67.85(10) C(3)-C(4)-(1) 70.30(11) C(4)-C(5)-C(1) 109.62(16) C(4)-C(5)-(1) 71.73(11) C(1)-C(5)-(1) 68.44(10) C(10)-C(6)-C(7) 104.91(16) C(10)-C(6)-Si(1) 117.92(13) C(7)-C(6)-Si(1) 120.09(14) C(10)-C(6)-(1) 69.46(10) C(7)-C(6)-(1) 69.80(10) Si(1)-C(6)-(1) 87.55(7) C(8)-C(7)-C(6) 109.40(17) C(8)-C(7)-(1) 71.34(11) C(6)-C(7)-(1) 68.22(10) C(9)-C(8)-C(7) 108.12(18) C(9)-C(8)-(1) 69.87(11) C(7)-C(8)-(1) 68.14(11) C(8)-C(9)-C(10) 107.86(18) C(8)-C(9)-(1) 70.13(11) C(10)-C(9)-(1) 67.93(11) C(9)-C(10)-C(6) 109.69(17) C(9)-C(10)-(1) 71.50(11) C(6)-C(10)-(1) 68.50(10) C(2)-C(11)-C(13) 109.47(16) C(2)-C(11)-C(12) 112.48(17) C(13)-C(11)-C(12) 110.73(18) C(16)-C(14)-Si(1) 114.52(16) C(17)-C(15)-Si(1) 114.38(15) S6

Me OAc (R) H Br Br Figure S2. 1 H NMR spectrum of (R,Sp)-2-[1-(acetoxy)ethyl]-1,1'-dibromoferrocene (crude) in CDCl3 with spectrometer frequency of 500.3 MHz. S7

* (CH 3 ) 2 O H 2 O Figure S3. 1 H NMR spectrum of Sp-3 in CDCl3 with spectrometer frequency of 500.3 MHz [ca. 1% of (Sp)-1-bromo-2-isopropylferrocene is present based on the peak at = 4.15 ppm denoted as *]. S8

Figure S4. 13 C NMR spectrum of Sp-3 in CDCl3 with spectrometer frequency of 125.8 MHz. S9

Figure S5. 1 H NMR spectrum of Sp-4 in C6D6 with spectrometer frequency of 500.3 MHz. S10

Figure S6. 13 C NMR spectrum of Sp-4 in C6D6 with spectrometer frequency of 125.8 MHz. S11

Figure S7. 29 Si NMR spectrum of Sp-4 in C6D6 with spectrometer frequency of 119.2 MHz. S12

Figure S8. 1 H NMR spectrum of rac-4 in C6D6 with spectrometer frequency of 500.3 MHz. S13

Figure S9. 13 C NMR spectrum of rac-4 in C6D6 with spectrometer frequency of 125.8 MHz. S14

Figure S10. 1 H NMR spectrum of rac-5 in C6D6 with spectrometer frequency of 600.2 MHz. S15

Figure S11. 13 C NMR spectrum of rac-5 in C6D6 with spectrometer frequency of 150.9 MHz. S16

Figure S12. 29 Si NMR spectrum of rac-5 in C6D6 with spectrometer frequency of 119.2 MHz. S17

Figure S13. 1 H NMR spectrum of (Sp-4)n in C6D6 with spectrometer frequency of 500.3 MHz. S18

Figure S14. 13 C NMR spectrum of (Sp-4)n in C6D6 with spectrometer frequency of 125.8 MHz. S19

Figure S15. 29 Si NMR spectrum of (Sp-4)n in C6D6 with spectrometer frequency of 119.2 MHz (see also Figure 5). S20

Figure S16. 1 H NMR spectrum of (rac-4)n in C6D6 with spectrometer frequency of 500.3 MHz. S21

Figure S17. 13 C NMR spectrum of (rac-4)n in C6D6 with spectrometer frequency of 125.8 MHz. S22

Figure S18. 29 Si NMR spectrum of (rac-4)n in C6D6 with spectrometer frequency of 119.2 MHz (see also Figure 5). S23

0.8 exotherm -0.2 Heat Flow (mw) -1.2 endotherm -2.2-3.2 50 70 90 110 130 150 170 190 210 230 Temperature ( C) Figure S19. Differential scanning calorimetry (DSC) thermogram of rac-4. The enthalpy of ΔH ROP = -72(±2) kj mol -1 is the average of three different measurements (ΔH ROP = -72.2, -72.9, and -72.1 kj mol -1 ; ±2 kj mol -1 is an estimated error; heating rate of 10 C min -1 ; melting endotherm at T (max) = 58 C; T ROP (onset) = 132 C; T ROP (max) = 162 C. S24

1.3 0.3 exotherm Heat Flow (mw) -0.7 endotherm -1.7 50 70 90 110 130 150 170 190 210 230 Temperature ( C) Figure S20. Differential scanning calorimetry (DSC) thermogram of Sp,Sp-4. The enthalpy of ΔH ROP = -62(±2) kj mol -1 is the average of three different measurements (ΔH ROP = -61.6, -62.4, and -60.8 kj mol -1 ; ±2 kj mol -1 is an estimated error; heating rate of 10 C min -1 ; melting endotherm at T (max) = 90 C; T ROP (onset) = 143 C; T ROP (max) = 164 C. S25

* * * * * Figure S21. GPC traces of polymer (rac-4)n (c = 12.9 mg/6.0 ml thf; Mw = 2.62 10 6 Da; Mn = 1.48 10 6 Da; Mw/Mn = 1.77). System peaks are indicated with *. S26

* * * * * * Figure S22. GPC traces of polymer (Sp-4)n (c = 16.5 mg/8.0 ml thf; Mw = 5.29 10 6 Da; Mn = 2.97 10 6 Da; Mw/Mn = 1.78). System peaks are indicated with *. S27

relative amounts based on the monomer: poly ipr Si*Me 2 through addition of monomer can give poly ( 29 Si) = -5.8 ppm ( 29 Si) = -6.7 ppm ( 29 Si) = -7.4 ppm ( 29 Si) = -8.2 ppm ipr Si Me 2 ipr + poly ipr Si Me 2 + poly ipr ipr Si Me 2 S p relative amount: 1 S p -Si-R p 1x1 S p -Si-Cp 1x2 S p -Si-S p 1x1 poly ipr Si*Me 2 can give ipr Si Si ipr Me 2 + ipr Me 2 + poly poly poly ipr Si Me 2 ipr relative amount: R p 1 R p -Si-S p 1x1 R p -Si-Cp 1x2 R p -Si-R p 1x1 poly ipr relative amount: Cp 2 Si*Me 2 ipr Si Me 2 poly ipr can give Si Cp-Si-S p Me 2 + poly 2x1 ipr Cp-Si-Cp 2x2 Si Me poly 2 ipr ipr Cp-Si-R p 2x1 statistical distribution for monomer of rac-4: 2 : 4 : 8 : 2 Figure S23. Illustration of a statistical distribution of 2 : 4 : 8 : 2 for the different environments around bridging SiMe2 moieties in (rac-4)n. Similar considerations for the starting monomer Sp-4 result in a statistical distribution of 0 : 1 : 2 : 1. S28

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