Cyclic polymers from alkynes

Size: px

Start display at page:

Download "Cyclic polymers from alkynes"

Sheryl White
5 years ago
Views:

1 DOI: /NCHEM.2516 Cyclic polymers from alkynes Christopher D. Roland, Hong Li, Khalil A. Abboud, Kenneth B. Wagener, and Adam S. Veige* University of Florida, Department of Chemistry, Center for Catalysis, P.O. Box , Gainesville, FL, Table of Contents 1. General Considerations Synthesis of NMR spectra of catalyst General Polymerization Procedure Polymerization Kinetics Data Light Scattering General Hydrogenation Procedure Ozonolysis of Cyclic Poly(phenylacetylene) Crystallography Data for NATURE CHEMISTRY 1

2 1. General Considerations. Unless specified otherwise, all manipulations were performed under an inert atmosphere using glove-box techniques. Toluene and pentane were dried using a GlassCountour drying column. Phenylacetylene was purchased from Sigma-Aldrich, distilled from magnesium sulfate, degassed by freeze pump thawing, and filtered through a column of basic alumina immediately prior to use. Toluene-d 8 was dried over phosphorous pentoxide (P 2 O 5 ), distilled, degassed by freeze pump thawing, and stored over 4Å molecular sieves. [ t BuOCO]W C( t Bu)(THF) 2 (1) was prepared according to literature procedure. 32 NMR spectra were obtained on Varian INOVA 500 MHz and Varian INOVA2 500 MHz spectrometers. Chemical shifts are reported in δ (ppm). For 1 H and 13 C NMR spectra, the residual solvent peaks were used as an internal reference. Molecular weight, radius of gyration and polydispersity were determined by size exclusion chromatography (SEC) in dimethylacetamide (DMAc) with 50 mm LiCl at 50 C and a flow rate of 1.0 ml/min (Agilent isocratic pump, degasser, and auto-sampler, columns: PLgel 5 μm guard + two ViscoGel I-series G3078 mixed bed columns: molecular weight range and g mol -1 ). Detection consisted of a Wyatt Optilab T-rEX refractive index detector operating at 658 nm and a Wyatt minidawn Treos light scattering detector operating at 659 nm. Absolute molecular weights and polydispersities were calculated using Wyatt ASTRA software. Intrinsic viscosity measurements were performed in THF at 35 C and a flow rate of 1.0 ml/min (Agilent isocratic pump, degasser, and autosampler; columns: three PLgel 5 μm MIXED-D mixed bed columns, molecular weight range ,000 g/mol). Detection consisted of a Wyatt Optilab rex refractive index detector operating at 658 nm, a Wyatt minidawn Treos light scattering detector operating at 656 nm, and a Wyatt ViscoStar-II viscometer. NATURE CHEMISTRY 2

3 2. Synthesis of 4. Synthesis of Catalyst 4. In a nitrogen filled glovebox, a glass vial equipped with a stir bar was charged with 1 (400 mg, 0.52 mmol) and dissolved in toluene (5.0 ml). 3,3- dimethyl-1-butyne (214 mg, 321 µl, 2.60 mmol) was added via micropipette with stirring. After 5 min, the solvent and residual 3,3-dimethyl-1-butyne were removed in vacuo to yield the light brown solid 4 in >99% yield (405 mg, 0.52 mmol). The resulting solid was dissolved in minimal pentane and cooled to -35 C to yield single crystals amenable to X-ray diffraction. 1 H NMR (500 MHz, C 7 D 8, δ (ppm)): (s, 1H, W- CH 32 ), 7.41 (d, 2H, Ar-H 8,10 ), 7.28 (dd, 2H, Ar-H 3,16 ), 7.26 (t, 1H, Ar-H 9 ), 7.19 (dd, 2H, Ar-H 5,14 ), 6.77 (t, 2H, Ar-H 4,15 ), 3.60 (t, 4H, THF-H 38,41 ), 1.66 (s, 9H, W-C-C(CH 3 ) 3 (H 29-31)), 1.20 (s, 18H, ligand C(CH 3 ) 3 (H 20-22,24-26 )), 1.16 (t, 4H, THF-H 39,40 ), 0.90 (s, 9H, W=C(CH 3 ) 3 (H )). 13 C NMR: (s, W=CC(CH 3 ) 3 (C 33 )), (s, WCCC(CH 3 ) 3 (C 27 )), (s, WCCC(CH 3 ) 3 (C 32 )), (s, C 1,18 ), (s, Ar-C 7,11 ), (s, Ar- C 6,13 ), (s, Ar-C 2,17 ), (s, Ar-C 12 ), (s, Ar-C 9 ), (s, Ar-C 8,10 ), (s, Ar-C 3,16 ), (s, Ar-C 5,14 ), (s, Ar-C 4,15 ), 71.3 (s, THF-C 38,41 ), 46.0 (s, W=CC(CH 3 ) 3 (C 34 )), 39.2 (s, WCCC(CH 3 ) 3 (C 28 )), 36.0 (s, W=CC(CH 3 ) 3 (C )), 34.3 (s, ligand C(CH 3 ) 3 (C 19,23 )), 31.1 (s, WCCC(CH 3 ) 3 (C )), 30.1 (s, ligand C(CH 3 ) 3 (C 20- NATURE CHEMISTRY 3

4 22,24-26)), (s, THF C 39,40 ). Anal. Calcd.: C: 63.24% H: 6.99%, Found: C: 63.28%, H: 7.09% Table S1. 1 H and 13 C NMR chemical shifts Position δ 1 H (ppm) δ 13 C (ppm) 1, , , , , , , , , , , , NATURE CHEMISTRY 4

5 3. NMR spectra of catalyst 4. Figure S1. 1 H NMR spectrum of catalyst 4. Figure S2. 1 H NMR spectrum (expanded) of catalyst 4. NATURE CHEMISTRY 5

6 Figure S3. 1 H NMR spectrum (expanded) of catalyst 4. Figure S4. 1 H- 13 C ghmbc spectrum of catalyst 4. NATURE CHEMISTRY 6

7 Figure S5. 1 H- 13 C ghmbc spectrum (expanded) of catalyst 4. Figure S6. 1 H- 13 C ghmbc spectrum (expanded) of catalyst 4. NATURE CHEMISTRY 7

8 Figure S7. 13 C{ 1 H} NMR spectrum of catalyst 4. Figure S8. 1 H- 1 H COSY spectrum of catalyst 4. NATURE CHEMISTRY 8

9 4. General Polymerization Procedure In an inert atmosphere glove box, toluene (2.0 ml) was added to a glass vial equipped with a stir bar. Phenylacetylene (218 µl, 2.00 mmol) was added via micropipete with stirring. A stock solution (1 mg/ml) of 4 (157 µl, 0.20 µmol) was added to the stirring solution in one shot to initiate polymerization. Polymerization was terminated via addition into tenfold excess of stirring anhydrous ether. The resulting polymer samples were isolated via vacuum filtration and residual solvent removed in vacuo. Table S2. Selected Polymerization Results Monomer [4]:[M] Time Yield Mn (kda) PDI Phenylacetylene 1: m30s 86.7% Phenylacetylene 1: m 94.1% Phenylacetylene 1: hrs 97.5% Phenylacetylene 1: m 96.4% Phenylacetylene 1: m 83.0% p-fluorophenylacetylene 1: m 88.0% p-fluorophenylacetylene 1: m 89.5% p-fluorophenylacetylene 1: m 91.5% p-methoxyphenylacetylene 1: m 81.3% p-methoxyphenylacetylene 1: m 78.1% p-methoxyphenylacetylene 1: m 96.3% NATURE CHEMISTRY 9

10 5. Polymerization Kinetics Data Table S3. Triplicate polymerization of phenylacetylene by 4. Trial 1 Trial 2 Trial 3 Time (s) Yield (mg) Yield (mg) Yield (mg) Average (mg) TON Time (min) Figure S9. Catalytic turnover number (TON) determined by quantitative yield of cyclic poly(phenylacetylene) vs. time (min) for 2, 3, and 4. All data shown in triplicate (averages shown). NATURE CHEMISTRY 10

11 6. Light Scattering Linear Cyclic Figure S10. GPC traces for molecular weight matched linear (red) and cyclic (blue) poly(phenylacetylene) used for light scattering measurements. Linear Number Average Diameter Cyclic Number Average Diameter Diameter (nm) Diameter (nm) Figure S11. Dynamic light scattering number average diameter measurements for linear (left) and cyclic (right) poly(phenylacetylene) samples. Table S4. RMS radius of gyration measurements and <RR gg 2 > cccccccccccc ratios <RR 2 gg > llllllllllll M n (Da) <R 2 g > 0.5 Linear (nm) <R 2 g > 0.5 Cyclic (nm) < RR 22 gg > cccccccccccc < RR 22 gg > llllllllllll 350, ± ± (6) 322, ± ± (7) 299, ± ± (10) 275, ± ± (10) 250, ± ± (11) 223, ± ± (12) NATURE CHEMISTRY 11

12 202, ± ± (15) 177, ± ± (17) 151, ± ± (18) 7. General Hydrogenation Procedure Hydrogenation was performed using a 150 ml Parr high-pressure stainless steel reaction vessel equipped with a 50 ml glass round bottom flask and a Teflon stirring bar. Unsaturated polymers were dissolved in anhydrous toluene and degassed for 1 h before adding Pd/C. The round bottom flask was placed into the reactor and then sealed. The Parr vessel was purged with 500 psi of H 2 three times. The pressure reactor was then charged to the desired psi, and the mixture was stirred. Catalyst was added every two days in the process. The resultant polymer was filtered through Celite and precipitated into cold methanol to obtain a solid, which was then filtered and transferred to a vial and dried under high vacuum (3 Χ 10-4 mmhg) overnight. Different hydrogenation conditions are shown in supplementary Table S4. Entry 1, 2, 3 are the conditions of partial hydrogenations and entry 4 is full hydrogenation conditions. Figure S12 shows the color of the polymer after different hydrogenation conditions. Table S5. Catalytic hydrogenation via Pd/C Entry Loading (wt%) Temperature ( C) Time (days) psi Color yellow 2 10, Light yellow 3 15, Trace color 4 15,15, white NATURE CHEMISTRY 12

(a) no hydrogenation, (b) Entry 1, Table S5, (c) Entry 2, Table

Stacked 1 H NMR spectra of cyclic poly(phenylacetylene) and

From top to bottom: unhydrogenated cyclic poly(phenylacetylene),

13 (a) (b) (c) (d) (e) Figure S12. Polymer generated from different hydrogenation conditions. (a) no hydrogenation, (b) Entry 1, Table S5, (c) Entry 2, Table S5, (d) Entry 3, Table S5, (e) Entry 4, Table S5 Figure S13: Stacked 1 H NMR spectra of cyclic poly(phenylacetylene) and partial hydrogenation. From top to bottom: unhydrogenated cyclic poly(phenylacetylene), partially hydrogenated sample from entry 2 of table S5, and partially hydrogenated phenylacetylene prior to ozonolysis. NATURE CHEMISTRY 13

14 8. Ozonolysis of Cyclic Poly(phenylacetylene) In a 50 ml one-neck flask equipped with a stir bar, were added 20 ml of dichloromethane and 0.1 g of polymer (Entry 3, Table S4). Ozone in oxygen was bubbled through the polymer solution, which was kept at -78 C during the whole process. Aliquots of the solution were taken at the 30 s and 16 min. The ozonolysis products were then reduced by slowly adding dimethyl sulfide at 0 C with stirring. The solution was then washed with deionized water and then a solution of brine, three times each. After extraction, the organic phase was dried over anhydrous sodium sulfate. The solvent was then removed in vacuo and the product was dried under high vacuum (3 Χ 10-4 mmhg) overnight. Figure S14. 1 H NMR spectra of partially hydrogenated cyclic poly(phenylacetylene) before and after ozonolysis. From top to bottom: no ozonolysis, ozonolysis for 30 s, ozonolysis for 16 min. NATURE CHEMISTRY 14

15 Figure S15. IR spectra of partially hydrogenated cyclic poly(phenylacetylene) before and after ozonolysis. Frombottom to top: no ozonolysis, ozonolysis for 30 s, ozonolysis for 16 min. The occurrence of the absorption peak at 1725 cm -1 after ozonolysis suggests the formation of aldehyde. Figure S16. 1 H NMR spectra of partially hydrogenated linear poly(phenylacetylene) before and after ozonolysis. From top to bottom: no ozonolysis, ozonolysis for 30 s, ozonolysis for 16 min. NATURE CHEMISTRY 15

16 Figure S17. IR spectra of partially hydrogenated linear poly(phenylacetylene) before and after ozonolysis. From bottom to top: no ozonolysis, ozonolysis for 30 s, ozonolysis for 16 min. The occurrence of the absorption peak at 1720 cm -1 after ozonolysis suggests the formation of aldehyde. Figure S18. DLS measurement for the ozonolysis of linear poly(phenylacetylene); no ozonolysis (blue), ozonolysis 30 s (red), ozonolysis 16 min (black). Cyclic polystyrene was generated as a white solid (Table S4 (e)) under the hydrogenation conditions listed in Entry 4, Table 4. The disappearance of the olefinic NATURE CHEMISTRY 16

17 proton signal at ~5.8 ppm, and the 3:5 proton integration ratio of aliphatic and aromatic protons confirms the exhaustive hydrogenation of cyclic poly(phenylacetylene) backbone. The resonance at 0.96 ppm suggests the formation of cyclohexyl moeity from hydrogenation of the phenyl groups. Figure S19. 1 H NMR spectrum of cyclic polystyrene. NATURE CHEMISTRY 17

18 9. Crystallography Data for 4 Figure S20. Molecular structure of 4 with ellipsoids drawn at the 50% probability level. NATURE CHEMISTRY 18

19 Experimental: X-Ray Intensity data were collected at 100 K on a Bruker DUO diffractometer using MoK radiation ( = Å) and an APEXII CCD area detector. The structure was deposited in the Cambridge Structural Database under # Raw data frames were read by program SAINT 1 and integrated using 3D profiling algorithms. The resulting data were reduced to produce hkl reflections and their intensities and estimated standard deviations. The data were corrected for Lorentz and polarization effects and numerical absorption corrections were applied based on indexed and measured faces. The structure was solved and refined in SHELXTL2013, using full-matrix leastsquares refinement. The non-h atoms were refined with anisotropic thermal parameters and all of the H atoms were calculated in idealized positions and refined riding on their parent atoms. Atom H32 on C32 was obtained from a Difference Fourier map and refined freely. In the final cycle of refinement, 9503 reflections (of which 8697 are observed with I > 2 (I)) were used to refine 461 parameters and the resulting R 1, wr 2 and S (goodness of fit) were 1.81%, 4.21% and 1.030, respectively. The refinement was carried out by minimizing the wr 2 function using F 2 rather than F values. R 1 is calculated to provide a reference to the conventional R value but its function is not minimized. Lattice toluene molecules were disordered and could not be modeled properly, thus program SQUEEZE, a part of the PLATON package of crystallographic software, was used to calculate the solvent disorder area and remove its contribution to the overall intensity data. Comment: checkcif identified an alert level B Isotropic non-h Atoms in Main Residue(s). Response: all non-h disordered atoms were refined with isotropic displacement parameters. NATURE CHEMISTRY 19

20 Table S6. Crystal data and structure refinement for cdr1. Identification code Empirical formula cdr1 Formula weight Temperature Wavelength Crystal system Space group P -1 C46 H66 O3 W 100(2) K Å Triclinic Unit cell dimensions a = (15) Å = (2). Volume (5) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 880 b = (17) Å = (2). c = (3) Å = (2). Crystal size x x mm 3 Theta range for data collection to Index ranges Reflections collected h 13, -14 k 14, -23 l 23 Independent reflections 9503 [R(int) = ] Completeness to theta = % Absorption correction Analytical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 9503 / 0 / 461 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = [8697] R indices (all data) R1 = , wr2 = Extinction coefficient Largest diff. peak and hole and e.å -3 R1 = ( Fo - Fc ) / Fo wr2 = [ w(fo 2 - Fc 2 ) 2 ] / w Fo 2 2 ]] 1/2 S = [ w(fo 2 - Fc 2 ) 2 ] / (n-p)] 1/2 w= 1/[ 2 (Fo 2 )+(m*p) 2 +n*p], p = [max(fo 2,0)+ 2* Fc 2 ]/3, m & n are constants. n/a NATURE CHEMISTRY 20

21 Table S7. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for cdr1. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) W(1) 3174(1) 994(1) 2598(1) 12(1) O(1) 2997(1) -283(1) 3129(1) 16(1) O(2) 4182(1) 2082(1) 2154(1) 16(1) O(3) 4942(1) -129(1) 2245(1) 19(1) C(1) 2620(2) -156(2) 3876(1) 16(1) C(2) 1705(2) -990(2) 3999(1) 18(1) C(3) 1386(2) -811(2) 4783(1) 22(1) C(4) 1943(2) 117(2) 5431(1) 24(1) C(5) 2847(2) 907(2) 5303(1) 21(1) C(6) 3188(2) 788(2) 4530(1) 18(1) C(7) 4184(2) 1639(2) 4418(1) 17(1) C(8) 5328(2) 1774(2) 4837(1) 21(1) C(9) 6276(2) 2560(2) 4737(1) 23(1) C(10) 6099(2) 3206(2) 4207(1) 20(1) C(11) 4958(2) 3111(2) 3787(1) 16(1) C(12) 3970(2) 2335(2) 3902(1) 15(1) C(13) 4798(2) 3866(2) 3260(1) 16(1) C(14) 5106(2) 5132(2) 3566(1) 20(1) C(15) 5016(2) 5858(2) 3087(1) 22(1) C(16) 4615(2) 5325(2) 2292(1) 21(1) C(17) 4296(2) 4065(2) 1951(1) 17(1) C(18) 4399(2) 3328(2) 2451(1) 15(1) C(19) 1078(2) -2057(2) 3312(1) 20(1) C(20) 2073(2) -2918(2) 2867(1) 24(1) C(21) 144(2) -2842(2) 3608(1) 26(1) C(22) 363(2) -1541(2) 2734(1) 21(1) C(23) 3835(2) 3532(2) 1074(1) 22(1) C(24) 2483(2) 3022(2) 1026(1) 26(1) C(25) 4675(2) 2511(2) 614(1) 31(1) C(26) 3850(2) 4516(2) 655(1) 33(1) NATURE CHEMISTRY 21

22 C(27) 2071(2) 90(2) 1607(1) 16(1) C(28) 1870(2) -925(2) 813(1) 18(1) C(29) 469(2) -1174(2) 598(1) 27(1) C(30) 2457(2) -2105(2) 857(1) 23(1) C(31) 2503(2) -500(2) 174(1) 25(1) C(32) 1471(2) 972(2) 2088(1) 17(1) C(33) 2689(2) 2291(2) 3496(1) 15(1) C(34) 1683(2) 3134(2) 3912(1) 17(1) C(35) 1334(2) 3954(2) 3410(1) 24(1) C(36) 2130(2) 3971(2) 4750(1) 29(1) C(37) 532(2) 2345(2) 3992(1) 22(1) C(38) 5869(7) 79(7) 1693(5) 22(2) C(39) 6671(6) -1033(6) 1566(4) 30(2) C(40) 6851(6) -929(6) 2443(4) 32(2) C(41) 5371(6) -1035(6) 2586(4) 18(1) C(38') 5691(5) -145(5) 1581(3) 23(1) C(39') 6991(5) -617(5) 1804(3) 38(1) C(40') 6490(4) -1577(4) 2155(3) 35(1) C(41') 5584(4) -716(5) 2761(3) 26(1) C(42) 8960(4) 5624(4) 862(2) 78(1) C(43) 8146(3) 5272(3) 1452(2) 61(1) C(44) 8563(2) 4172(3) 1657(2) 42(1) C(45) 7742(3) 3803(3) 2227(2) 55(1) C(46) 8085(3) 2654(3) 2387(2) 45(1) NATURE CHEMISTRY 22

23 Table S8. Bond lengths [Å] and angles [ ] for 4. W(1)-C(33) (19) C(15)-C(16) 1.393(3) W(1)-O(2) (13) C(16)-C(17) 1.400(3) W(1)-O(1) (13) C(17)-C(18) 1.416(3) W(1)-C(32) 2.014(2) C(17)-C(23) 1.538(3) W(1)-C(27) (19) C(19)-C(21) 1.538(3) W(1)-O(3) (14) C(19)-C(22) 1.541(3) W(1)-C(12) (18) C(19)-C(20) 1.543(3) O(1)-C(1) 1.363(2) C(23)-C(24) 1.536(3) O(2)-C(18) 1.364(2) C(23)-C(25) 1.539(3) O(3)-C(38') 1.445(5) C(23)-C(26) 1.540(3) O(3)-C(41) 1.446(6) C(27)-C(32) 1.304(3) O(3)-C(41') 1.473(4) C(27)-C(28) 1.516(3) O(3)-C(38) 1.486(7) C(28)-C(29) 1.535(3) C(1)-C(6) 1.412(3) C(28)-C(31) 1.539(3) C(1)-C(2) 1.417(3) C(28)-C(30) 1.541(3) C(2)-C(3) 1.398(3) C(32)-H(32) 0.94(2) C(2)-C(19) 1.538(3) C(33)-C(34) 1.525(3) C(3)-C(4) 1.392(3) C(34)-C(36) 1.539(3) C(4)-C(5) 1.377(3) C(34)-C(35) 1.541(3) C(5)-C(6) 1.398(3) C(34)-C(37) 1.542(3) C(6)-C(7) 1.483(3) C(38)-C(39) 1.530(9) C(7)-C(8) 1.395(3) C(39)-C(40) 1.530(9) C(7)-C(12) 1.416(3) C(40)-C(41) 1.625(8) C(8)-C(9) 1.388(3) C(38')-C(39') 1.604(7) C(9)-C(10) 1.386(3) C(39')-C(40') 1.520(7) C(10)-C(11) 1.400(3) C(40')-C(41') 1.594(6) C(11)-C(12) 1.422(3) C(42)-C(43) 1.527(4) C(11)-C(13) 1.477(3) C(43)-C(44) 1.504(4) C(12)-C(33) 1.527(3) C(44)-C(45) 1.511(4) C(13)-C(14) 1.400(3) C(45)-C(46) 1.495(4) C(13)-C(18) 1.414(3) C(33)-W(1)-O(2) 95.07(7) C(14)-C(15) 1.375(3) C(33)-W(1)-O(1) 94.09(7) O(2)-W(1)-O(1) (6) C(5)-C(4)-C(3) (19) NATURE CHEMISTRY 23

24 C(33)-W(1)-C(32) 88.51(8) C(4)-C(5)-C(6) (19) O(2)-W(1)-C(32) (7) C(5)-C(6)-C(1) (18) O(1)-W(1)-C(32) (7) C(5)-C(6)-C(7) (18) C(33)-W(1)-C(27) (8) C(1)-C(6)-C(7) (17) O(2)-W(1)-C(27) 98.73(6) C(8)-C(7)-C(12) (18) O(1)-W(1)-C(27) 96.83(6) C(8)-C(7)-C(6) (18) C(32)-W(1)-C(27) 37.47(8) C(12)-C(7)-C(6) (17) C(33)-W(1)-O(3) (7) C(9)-C(8)-C(7) (19) O(2)-W(1)-O(3) 78.80(5) C(10)-C(9)-C(8) (19) O(1)-W(1)-O(3) 76.54(5) C(9)-C(10)-C(11) (19) C(32)-W(1)-O(3) (7) C(10)-C(11)-C(12) (18) C(27)-W(1)-O(3) 97.95(7) C(10)-C(11)-C(13) (17) C(33)-W(1)-C(12) 38.76(7) C(12)-C(11)-C(13) (17) O(2)-W(1)-C(12) 86.24(6) C(7)-C(12)-C(11) (17) O(1)-W(1)-C(12) 84.74(6) C(7)-C(12)-C(33) (17) C(32)-W(1)-C(12) (7) C(11)-C(12)-C(33) (17) C(27)-W(1)-C(12) (7) C(7)-C(12)-W(1) (12) O(3)-W(1)-C(12) 97.31(6) C(11)-C(12)-W(1) (13) C(1)-O(1)-W(1) (11) C(33)-C(12)-W(1) 51.26(9) C(18)-O(2)-W(1) (12) C(14)-C(13)-C(18) (18) C(38')-O(3)-C(41') 110.4(3) C(14)-C(13)-C(11) (17) C(41)-O(3)-C(38) 109.8(4) C(18)-C(13)-C(11) (16) C(38')-O(3)-W(1) 124.9(2) C(15)-C(14)-C(13) (19) C(41)-O(3)-W(1) 125.6(2) C(14)-C(15)-C(16) (18) C(41')-O(3)-W(1) (18) C(15)-C(16)-C(17) (19) C(38)-O(3)-W(1) 124.3(3) C(16)-C(17)-C(18) (18) O(1)-C(1)-C(6) (17) C(16)-C(17)-C(23) (18) O(1)-C(1)-C(2) (17) C(18)-C(17)-C(23) (17) C(6)-C(1)-C(2) (18) O(2)-C(18)-C(13) (17) C(3)-C(2)-C(1) (18) O(2)-C(18)-C(17) (17) C(3)-C(2)-C(19) (18) C(13)-C(18)-C(17) (17) C(1)-C(2)-C(19) (17) C(2)-C(19)-C(21) (17) C(4)-C(3)-C(2) (19) C(2)-C(19)-C(22) (16) C(21)-C(19)-C(22) (17) C(12)-C(33)-W(1) 89.98(11) C(2)-C(19)-C(20) (17) C(33)-C(34)-C(36) (16) NATURE CHEMISTRY 24

25 C(21)-C(19)-C(20) (16) C(33)-C(34)-C(35) (16) C(22)-C(19)-C(20) (17) C(36)-C(34)-C(35) (17) C(24)-C(23)-C(17) (16) C(33)-C(34)-C(37) (15) C(24)-C(23)-C(25) (18) C(36)-C(34)-C(37) (17) C(17)-C(23)-C(25) (18) C(35)-C(34)-C(37) (16) C(24)-C(23)-C(26) (18) O(3)-C(38)-C(39) 101.7(5) C(17)-C(23)-C(26) (17) C(40)-C(39)-C(38) 96.9(6) C(25)-C(23)-C(26) (18) C(39)-C(40)-C(41) 94.8(5) C(32)-C(27)-C(28) (19) O(3)-C(41)-C(40) 99.4(4) C(32)-C(27)-W(1) 69.95(12) O(3)-C(38')-C(39') 103.0(3) C(28)-C(27)-W(1) (15) C(40')-C(39')-C(38') 98.8(4) C(27)-C(28)-C(29) (17) C(39')-C(40')-C(41') 97.2(4) C(27)-C(28)-C(31) (16) O(3)-C(41')-C(40') 101.3(3) C(29)-C(28)-C(31) (17) C(44)-C(43)-C(42) 114.0(3) C(27)-C(28)-C(30) (16) C(43)-C(44)-C(45) 114.1(3) C(29)-C(28)-C(30) (16) C(46)-C(45)-C(44) 114.8(3) C(31)-C(28)-C(30) (17) W(1)-C(32)-H(32) 150.5(13) C(27)-C(32)-W(1) 72.58(12) C(34)-C(33)-C(12) (16) C(27)-C(32)-H(32) 136.9(13) C(34)-C(33)-W(1) (14) Symmetry transformations used to generate equivalent atoms: NATURE CHEMISTRY 25

26 Table S9. Anisotropic displacement parameters (Å 2 x 10 3 ) for cdr1. The anisotropic displacement factor exponent takes the form: - 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 W(1) 14(1) 10(1) 12(1) 4(1) 2(1) 1(1) O(1) 19(1) 13(1) 15(1) 6(1) 5(1) 4(1) O(2) 17(1) 12(1) 17(1) 4(1) 3(1) 0(1) O(3) 18(1) 20(1) 20(1) 9(1) 5(1) 5(1) C(1) 20(1) 14(1) 17(1) 8(1) 4(1) 8(1) C(2) 21(1) 15(1) 20(1) 8(1) 6(1) 9(1) C(3) 24(1) 22(1) 27(1) 15(1) 11(1) 9(1) C(4) 32(1) 28(1) 18(1) 12(1) 10(1) 13(1) C(5) 29(1) 20(1) 16(1) 7(1) 2(1) 10(1) C(6) 22(1) 15(1) 18(1) 8(1) 3(1) 8(1) C(7) 23(1) 13(1) 13(1) 1(1) 3(1) 6(1) C(8) 28(1) 17(1) 18(1) 4(1) -1(1) 7(1) C(9) 23(1) 20(1) 22(1) 1(1) -6(1) 4(1) C(10) 19(1) 15(1) 21(1) 0(1) 0(1) 1(1) C(11) 19(1) 13(1) 14(1) 0(1) 2(1) 4(1) C(12) 19(1) 12(1) 12(1) 0(1) 1(1) 4(1) C(13) 12(1) 14(1) 20(1) 5(1) 4(1) 2(1) C(14) 18(1) 16(1) 21(1) 2(1) 1(1) 0(1) C(15) 23(1) 13(1) 30(1) 6(1) 3(1) -1(1) C(16) 22(1) 17(1) 26(1) 11(1) 6(1) 2(1) C(17) 14(1) 18(1) 20(1) 6(1) 6(1) 1(1) C(18) 11(1) 13(1) 20(1) 4(1) 4(1) 1(1) C(19) 22(1) 14(1) 24(1) 7(1) 7(1) 2(1) C(20) 26(1) 16(1) 31(1) 7(1) 8(1) 4(1) C(21) 30(1) 19(1) 32(1) 11(1) 10(1) 1(1) C(22) 21(1) 19(1) 26(1) 9(1) 4(1) 0(1) C(23) 28(1) 22(1) 19(1) 10(1) 4(1) -2(1) C(24) 28(1) 29(1) 26(1) 16(1) -5(1) -6(1) C(25) 39(1) 32(1) 20(1) 5(1) 9(1) 0(1) C(26) 49(2) 32(1) 23(1) 17(1) 1(1) -8(1) NATURE CHEMISTRY 26

27 C(27) 20(1) 16(1) 16(1) 9(1) 0(1) -3(1) C(29) 24(1) 29(1) 25(1) 7(1) -6(1) -3(1) C(30) 30(1) 17(1) 21(1) 2(1) 0(1) 1(1) C(31) 33(1) 24(1) 16(1) 5(1) 3(1) -2(1) C(32) 17(1) 16(1) 18(1) 7(1) 1(1) 0(1) C(33) 16(1) 13(1) 16(1) 7(1) 0(1) 0(1) C(34) 18(1) 14(1) 19(1) 4(1) 3(1) 4(1) C(35) 22(1) 16(1) 36(1) 11(1) 4(1) 5(1) C(36) 28(1) 27(1) 25(1) -4(1) 2(1) 9(1) C(37) 21(1) 23(1) 25(1) 10(1) 8(1) 5(1) C(42) 84(3) 85(3) 55(2) 18(2) -13(2) -52(2) C(43) 44(2) 75(2) 70(2) 36(2) -13(2) -12(2) C(44) 32(1) 49(2) 33(1) -1(1) 1(1) -10(1) C(45) 32(2) 71(2) 72(2) 33(2) 17(1) 18(1) C(46) 37(2) 53(2) 40(2) 9(1) -3(1) 1(1) 1 K. P. McGowan, M. E. O'Reilly, I. Ghiviriga, K. A. Abboud and A. S. Veige, Chem. Sci., 2013, 2013, NATURE CHEMISTRY 27

1. General Considerations.

Highly Tactic Cyclic Polynorbornene: Stereoselective Ring Expansion Metathesis Polymerization (REMP) of Norbornene Catalyzed By a New Tethered Tungstenalkylidene Catalyst Table of Contents 1. General Considerations....