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Supporting Information for
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 117200, Gainesville, FL, 32611.
Table of Contents
1. General Considerations. ........................................................................................... 2
2. Synthesis of 4. ............................................................................................................ 3
3. NMR spectra of catalyst 4. ....................................................................................... 5
4. General Polymerization Procedure ......................................................................... 9
5. Polymerization Kinetics Data ................................................................................ 10
6. Light Scattering ....................................................................................................... 11
7. General Hydrogenation Procedure ....................................................................... 12
8. Ozonolysis of Cyclic Poly(phenylacetylene).......................................................... 14
9. Crystallography Data for 4 .................................................................................... 18
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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-d8 was dried over phosphorous pentoxide (P2O5), distilled,
degassed by freeze pump thawing, and stored over 4Å molecular sieves.
[tBuOCO]W≡C(tBu)(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 1H and 13C 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 0-20 × 103 and 0-
100 × 104 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 200−400,000 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.
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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. 1H NMR (500 MHz, C7D8, δ (ppm)): 11.61 (s, 1H, W-
CH32), 7.41 (d, 2H, Ar-H8,10), 7.28 (dd, 2H, Ar-H3,16), 7.26 (t, 1H, Ar-H9), 7.19 (dd, 2H,
Ar-H5,14), 6.77 (t, 2H, Ar-H4,15), 3.60 (t, 4H, THF-H38,41), 1.66 (s, 9H, W-C-C(CH3)3 (H29-
31)), 1.20 (s, 18H, ligand C(CH3)3 (H20-22,24-26)), 1.16 (t, 4H, THF-H39,40), 0.90 (s, 9H,
W=C(CH3)3 (H35-37)). 13C NMR: 268.8 (s, W=CC(CH3)3 (C33)), 213.0 (s, WCCC(CH3)3
(C27)), 184.0 (s, WCCC(CH3)3 (C32)), 168.5 (s, C1,18), 153.7 (s, Ar-C7,11), 137.4 (s, Ar-
C6,13), 137.3 (s, Ar-C2,17), 132.5 (s, Ar-C12), 130.9 (s, Ar-C9), 129.2 (s, Ar-C8,10), 128.2 (s,
Ar-C3,16), 125.7 (s, Ar-C5,14), 118.7 (s, Ar-C4,15), 71.3 (s, THF-C38,41), 46.0 (s,
W=CC(CH3)3 (C34)), 39.2 (s, WCCC(CH3)3 (C28)), 36.0 (s, W=CC(CH3)3 (C35-37)), 34.3
(s, ligand C(CH3)3 (C19,23)), 31.1 (s, WCCC(CH3)3 (C29-31)), 30.1 (s, ligand C(CH3)3 (C20-
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22,24-26)), 25.00 (s, THF C39,40). Anal. Calcd.: C: 63.24% H: 6.99%, Found: C: 63.28%, H:
7.09%
Table S1. 1H and 13C NMR chemical shifts Position δ1H (ppm) δ13C (ppm)
1, 18 - 168.5 2, 17 - 137.3 3, 16 7.28 128.2 4, 15 6.77 118.7 5, 14 7.19 125.7 6, 13 - 137.4 7, 11 - 153.7 8, 10 7.41 129.2
9 7.26 130.9 12 - 132.5
19, 23 - 34.3 20-22, 24-26 1.20 30.1
27 - 213.0 28 - 39.2
29-31 1.66 31.1 32 11.61 184.0 33 - 268.8 34 - 46.0
35-37 0.90 36.0 38, 41 3.60 71.3 39, 40 1.16 25.0
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3. NMR spectra of catalyst 4.
Figure S1. 1H NMR spectrum of catalyst 4.
Figure S2. 1H NMR spectrum (expanded) of catalyst 4.
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Figure S3. 1H NMR spectrum (expanded) of catalyst 4.
Figure S4. 1H-13C gHMBC spectrum of catalyst 4.
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Figure S5. 1H-13C gHMBC spectrum (expanded) of catalyst 4.
Figure S6. 1H-13C gHMBC spectrum (expanded) of catalyst 4.
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Figure S7. 13C{1H} NMR spectrum of catalyst 4.
Figure S8. 1H-1H COSY spectrum of catalyst 4.
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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 1:10000 2m30s 86.7% 35.3 2.19
Phenylacetylene 1:10000 15m 94.1% 30.8 2.23
Phenylacetylene 1:10000 24hrs 97.5% 30.4 2.03
Phenylacetylene 1:5000 15m 96.4% 68.9 1.75
Phenylacetylene 1:10000 15m 83.0% 57.9 1.66
p-fluorophenylacetylene 1:1000 75m 88.0% 22.5 1.93
p-fluorophenylacetylene 1:1000 120m 89.5% 20.9 1.90
p-fluorophenylacetylene 1:1000 150m 91.5% 21.0 1.99
p-methoxyphenylacetylene 1:1000 135m 81.3% 5.4 1.59
p-methoxyphenylacetylene 1:1000 150m 78.1% 6.1 1.61
p-methoxyphenylacetylene 1:1000 165m 96.3% 6.6 1.65
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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)
30 50 34 67 50.3
150 77 73 75 75.0
300 98 93 90 93.7
600 111 133 104 116.0
900 134 146 168 149.3
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).
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
0 5 10 15 20
TON
Time (min)
2
4
3
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6. Light Scattering
Figure S10. GPC traces for molecular weight matched linear (red) and cyclic (blue) poly(phenylacetylene) used for light scattering measurements.
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 <𝑅𝑅𝑔𝑔2>𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐<𝑅𝑅𝑔𝑔2>𝑐𝑐𝑐𝑐𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙
ratios
Mn (Da) <Rg2>0.5
Linear (nm) <Rg2>0.5
Cyclic (nm) < 𝑹𝑹𝒈𝒈
𝟐𝟐 >𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄
< 𝑹𝑹𝒈𝒈𝟐𝟐 >𝒄𝒄𝒄𝒄𝒍𝒍𝒍𝒍𝒍𝒍𝒍𝒍
350,000 20.4 ± 0.4 14.8 ± 1.3 0.52(6) 322,000 18.8 ± 0.5 14.4 ± 1.3 0.58(7) 299,000 17.4 ± 0.6 14 ± 1.5 0.64(10) 275,000 16.7 ± 0.5 13.4 ± 1.4 0.64(10) 250,000 15.9 ± 1.0 12.9 ± 1.4 0.65(11) 223,000 15.2 ± 1.0 12.1 ± 1.5 0.63(12)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
12 13 14 15 16 17 18 19
Linear
Cyclic
1 10 100Diameter (nm)
Linear Number Average Diameter
1 10 100Diameter (nm)
Cyclic Number Average Diameter
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202,000 14.4 ± 1.3 11.6 ± 1.5 0.65(15) 177,000 13.5 ± 1.4 10.8 ± 1.8 0.64(17) 151,000 12.8 ± 1.5 9.8 ± 1.9 0.58(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 H2 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
1 10 75 2 750 yellow
2 10,10 75 4 900 Light yellow
3 15,15 90 5 900 Trace color
4 15,15,15 90 6 900 white
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(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 1H 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.
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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. 1H 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.
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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. 1H 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.
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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
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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. 1H NMR spectrum of cyclic polystyrene.
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9. Crystallography Data for 4
Figure S20. Molecular structure of 4 with ellipsoids drawn at the 50% probability level.
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Experimental: X-Ray Intensity data were collected at 100 K on a Bruker DUO
diffractometer using MoK radiation ( = 0.71073 Å) and an APEXII CCD area detector.
The structure was deposited in the Cambridge Structural Database under # 1046062
Raw data frames were read by program SAINT1 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 least-
squares 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 R1, wR2
and S (goodness of fit) were 1.81%, 4.21% and 1.030, respectively. The refinement was
carried out by minimizing the wR2 function using F2 rather than F values. R1 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.
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Table S6. Crystal data and structure refinement for cdr1.
Identification code cdr1
Empirical formula C46 H66 O3 W
Formula weight 850.83
Temperature 100(2) K
Wavelength 0.71073 Å
Crystal system Triclinic
Space group P -1
Unit cell dimensions a = 10.7569(15) Å = 108.810(2)°.
b = 11.4834(17) Å = 91.728(2)°.
c = 17.772(3) Å = 92.276(2)°.
Volume 2074.3(5) Å3
Z 2
Density (calculated) 1.346 Mg/m3
Absorption coefficient 2.822 mm-1
F(000) 880
Crystal size 0.184 x 0.094 x 0.046 mm3
Theta range for data collection 1.875 to 27.500°.
Index ranges -13≤h≤13, -14≤k≤14, -23≤l≤23
Reflections collected 35543
Independent reflections 9503 [R(int) = 0.0323]
Completeness to theta = 25.242° 100.0 %
Absorption correction Analytical
Max. and min. transmission 0.8998 and 0.7214
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 9503 / 0 / 461
Goodness-of-fit on F2 1.030
Final R indices [I>2sigma(I)] R1 = 0.0181, wR2 = 0.0421 [8697]
R indices (all data) R1 = 0.0215, wR2 = 0.0429
Extinction coefficient n/a
Largest diff. peak and hole 1.026 and -0.506 e.Å-3 R1 = (||Fo| - |Fc||) / |Fo|
wR2 = [w(Fo2 - Fc2)2] / wFo22]]1/2
S = [w(Fo2 - Fc2)2] / (n-p)]1/2
w= 1/[2(Fo2)+(m*p)2+n*p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants.
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Table S7. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)
for cdr1. U(eq) is defined as one third of the trace of the orthogonalized Uij 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)
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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)
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Table S8. Bond lengths [Å] and angles [°] for 4.
_____________________________________________________
W(1)-C(33) 1.9021(19) C(15)-C(16) 1.393(3)
W(1)-O(2) 1.9844(13) C(16)-C(17) 1.400(3)
W(1)-O(1) 1.9903(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) 2.0454(19) C(19)-C(21) 1.538(3)
W(1)-O(3) 2.3279(14) C(19)-C(22) 1.541(3)
W(1)-C(12) 2.4385(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) 152.37(6) C(5)-C(4)-C(3) 119.25(19)
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C(33)-W(1)-C(32) 88.51(8) C(4)-C(5)-C(6) 120.34(19)
O(2)-W(1)-C(32) 102.55(7) C(5)-C(6)-C(1) 120.14(18)
O(1)-W(1)-C(32) 103.69(7) C(5)-C(6)-C(7) 118.76(18)
C(33)-W(1)-C(27) 125.92(8) C(1)-C(6)-C(7) 121.07(17)
O(2)-W(1)-C(27) 98.73(6) C(8)-C(7)-C(12) 119.97(18)
O(1)-W(1)-C(27) 96.83(6) C(8)-C(7)-C(6) 119.68(18)
C(32)-W(1)-C(27) 37.47(8) C(12)-C(7)-C(6) 120.34(17)
C(33)-W(1)-O(3) 136.07(7) C(9)-C(8)-C(7) 120.65(19)
O(2)-W(1)-O(3) 78.80(5) C(10)-C(9)-C(8) 120.02(19)
O(1)-W(1)-O(3) 76.54(5) C(9)-C(10)-C(11) 120.99(19)
C(32)-W(1)-O(3) 135.41(7) C(10)-C(11)-C(12) 119.38(18)
C(27)-W(1)-O(3) 97.95(7) C(10)-C(11)-C(13) 118.81(17)
C(33)-W(1)-C(12) 38.76(7) C(12)-C(11)-C(13) 121.76(17)
O(2)-W(1)-C(12) 86.24(6) C(7)-C(12)-C(11) 118.89(17)
O(1)-W(1)-C(12) 84.74(6) C(7)-C(12)-C(33) 120.84(17)
C(32)-W(1)-C(12) 127.27(7) C(11)-C(12)-C(33) 120.24(17)
C(27)-W(1)-C(12) 164.60(7) C(7)-C(12)-W(1) 110.48(12)
O(3)-W(1)-C(12) 97.31(6) C(11)-C(12)-W(1) 108.16(13)
C(1)-O(1)-W(1) 128.67(11) C(33)-C(12)-W(1) 51.26(9)
C(18)-O(2)-W(1) 128.62(12) C(14)-C(13)-C(18) 119.84(18)
C(38')-O(3)-C(41') 110.4(3) C(14)-C(13)-C(11) 118.62(17)
C(41)-O(3)-C(38) 109.8(4) C(18)-C(13)-C(11) 121.48(16)
C(38')-O(3)-W(1) 124.9(2) C(15)-C(14)-C(13) 120.43(19)
C(41)-O(3)-W(1) 125.6(2) C(14)-C(15)-C(16) 119.49(18)
C(41')-O(3)-W(1) 123.66(18) C(15)-C(16)-C(17) 122.78(19)
C(38)-O(3)-W(1) 124.3(3) C(16)-C(17)-C(18) 117.08(18)
O(1)-C(1)-C(6) 119.22(17) C(16)-C(17)-C(23) 120.50(18)
O(1)-C(1)-C(2) 120.54(17) C(18)-C(17)-C(23) 122.41(17)
C(6)-C(1)-C(2) 120.19(18) O(2)-C(18)-C(13) 118.72(17)
C(3)-C(2)-C(1) 117.04(18) O(2)-C(18)-C(17) 120.78(17)
C(3)-C(2)-C(19) 120.39(18) C(13)-C(18)-C(17) 120.40(17)
C(1)-C(2)-C(19) 122.57(17) C(2)-C(19)-C(21) 112.15(17)
C(4)-C(3)-C(2) 123.01(19) C(2)-C(19)-C(22) 109.83(16)
C(21)-C(19)-C(22) 107.78(17) C(12)-C(33)-W(1) 89.98(11)
C(2)-C(19)-C(20) 109.76(17) C(33)-C(34)-C(36) 111.95(16)
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C(21)-C(19)-C(20) 107.24(16) C(33)-C(34)-C(35) 108.54(16)
C(22)-C(19)-C(20) 110.02(17) C(36)-C(34)-C(35) 108.46(17)
C(24)-C(23)-C(17) 109.40(16) C(33)-C(34)-C(37) 109.41(15)
C(24)-C(23)-C(25) 110.42(18) C(36)-C(34)-C(37) 108.34(17)
C(17)-C(23)-C(25) 110.32(18) C(35)-C(34)-C(37) 110.14(16)
C(24)-C(23)-C(26) 107.21(18) O(3)-C(38)-C(39) 101.7(5)
C(17)-C(23)-C(26) 112.11(17) C(40)-C(39)-C(38) 96.9(6)
C(25)-C(23)-C(26) 107.31(18) C(39)-C(40)-C(41) 94.8(5)
C(32)-C(27)-C(28) 139.75(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) 150.28(15) C(40')-C(39')-C(38') 98.8(4)
C(27)-C(28)-C(29) 109.72(17) C(39')-C(40')-C(41') 97.2(4)
C(27)-C(28)-C(31) 108.43(16) O(3)-C(41')-C(40') 101.3(3)
C(29)-C(28)-C(31) 109.36(17) C(44)-C(43)-C(42) 114.0(3)
C(27)-C(28)-C(30) 109.78(16) C(43)-C(44)-C(45) 114.1(3)
C(29)-C(28)-C(30) 110.18(16) C(46)-C(45)-C(44) 114.8(3)
C(31)-C(28)-C(30) 109.34(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) 121.20(16)
C(27)-C(32)-H(32) 136.9(13) C(34)-C(33)-W(1) 148.79(14)
________________________
Symmetry transformations used to generate equivalent atoms:
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Table S9. Anisotropic displacement parameters (Å2x 103) for cdr1. The anisotropic
displacement factor exponent takes the form: - 2[ h2 a*2U11 + ... + 2 h k a* b* U12 ]
______________________________________________________________________________
U11 U22 U33 U23 U13 U12
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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)
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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, 1145-1155.