Enolesters as chain end-functionalizing agents for the living ring opening metathesis polymerization

Supporting Information for

Enolesters as chain end-functionalizing agents for the living ring opening

metathesis polymerization

Peng Liu, Mohammad Yasir, Helena Kurzen, Nils Hanik, Mark Schäfer and Andreas

F.M. Kilbinger*

University of Fribourg, Chemistry Department, Chemin du Musée 9, CH-1700

Fribourg

E-mail: andreas.kilbinger@unifr.ch

Experimental

1

_{H NMR reaction of G1 benzylidene with cis/trans-BAc as terminating agent}

Figure S1 Reaction between G1 and but-1-en-1-yl acetate (BAc). Spectra from bottom to top: 0h, 3h, 6h and 96h.

For clarity the full spectral window is not shown. Carbene signals from the residual initiator complex (20.01 ppm in 1_{H NMR spectra in methylene chloride-d}

2, 400 MHz) are present at all times. trans- But-1-en-1-yl acetate at

7.05 ppm (d, J = 12.7 Hz), cis-but-1-en-1-yl acetate at 6.94 ppm (d, J = 6.7 Hz), (Z/E)-but-1-en-1-ylbenzene at 6.38 ppm (d, J = 16.1 Hz, E/Z = 87:13).

Table S1 Ring-opening Metathesis Polymerization of Different Monomers with Different Catalysts and

Terminating-Agents (TA).

Entry Monomer Catalyst Terminating

agent

Mon:Cat:TA M

[kDa] M

[kDa] PDI

1

MNI

G1

vinyl

acetate

17:1:50

3000

5400

1.23

2

_MNI

_G1

_{vinyl ether}

_17:1:50

₃₀₀₀

₅₃₀₀

_1.26

3

_MNI

_G1

₁

_17:1:50

₃₀₀₀

₅₈₀₀

_1.21

4

MNI

G1

4

10:1:5

1800

3900

1.12

5

MNI

G1

4

20:1:5

3500

5400

1.18

6

_MNI

_G1

₄

_30:1:5

₅₃₀₀

₆₈₀₀

_1.18

7

_MNI

_G1

₆

_20:1:5

₃₅₀₀

₅₈₀₀

_1.18

8

HNI

G1

4

20:1:5

3500

5200

1.16

9

OMNI

G1

4

20:1:5

3500

3200

1.11

10

MNI

G3

4

10:1:5

1800

2500

1.11

11

MNI

G3

4

20:1:5

3500

6500

1.17

12

MNI

G3

4

30:1:5

5300

11300

1.15

a _{Mn were obtained from GPC in THF vs polystyrene standards, RI detector.}

b _{Mn were obtained from GPC in Chloroform vs polystyrene standards, RI detector and the produce for}

synthesizing Polymers 10-12 is the same with Polymers 4-6.

c _{Exo-N-methyl-7-oxanorbornene-2,3-dicarboximide}

Table S2 Time-resolved termination reaction of MNI and 4 with G1 in CD2Cl2a followed by 1H NMR

spectroscopy.

a _{G1 (8.23 mg) was dissolved in 0.5 ml CD2Cl2, then MNI (10 mg) was added. After 1h, terminating agent 4}

(dissolved in 0.1 ml of CD2Cl2) was added at t0. The concentration of the propagating Ru carbene signal

(1_{H-NMR, 400 MHz) was integrated with respect to residual protonated solvent. “0” indicates that no}

Eq.

5min 10min 20min 30min 40min 50min 60min 90min 120min

1eq

4.40

1.90

1.12

0.64

0.47

0.22

0.1

0

0

5eq

0.11

0

0

0

-

-

-

-

-

10eq

0

0

0

0

-

-

-

-

-

NMR Spectra

Figure S4 1_{H-NMR spectrum(400 MHz, CDCl3) of 2}

Figure S6 1_{H-NMR spectrum(400 MHz, CDCl3) of 3}

Figure S7 13_{C-NMR spectrum(101 MHz, CDCl}

Figure S8 1_{H-NMR spectrum(400 MHz, CDCl3) of 4}

Figure S9 13_{C-NMR spectrum(101 MHz, CDCl}

Figure S10 1_{H-NMR spectrum(400 MHz, CDCl3) of 5}

Figure S11 13_{C-NMR spectrum(101 MHz, CDCl}

Figure S12 1_{H-NMR spectrum(400 MHz, CDCl3) of 6}

Figure S13 13_{C-NMR spectrum(101 MHz, CDCl}

Figure S14 1_{H-NMR spectrum(300 MHz, CDCl3) of Polymer 1}

Figure S16 1_{H-NMR spectrum(300 MHz, CDCl3) of Polymer 2}

Figure S18 1_{H-NMR spectrum(300 MHz, CDCl3) of Polymer 3}

Figure S20 1_{H-NMR spectrum(400 MHz, CDCl3) of Polymer 4}

Figure S22 1_{H-NMR spectrum(400 MHz, CDCl3) of Polymer 5}

Figure S24 1_{H-NMR spectrum(400 MHz, CDCl3) of Polymer 6}

Figure S26 1_{H-NMR spectrum(400 MHz, CDCl3) of Polymer 7}

Figure S28 1_{H-NMR spectrum(400 MHz, CDCl3) of Polymer 8}

Figure S30 1_{H-NMR spectrum(400 MHz, CDCl3) of Polymer 9}

MALDI-ToF spectrometric data of Polymers

Figure S32 MALDI-ToF mass spectrum (DCTB, NaTFA) of Polymer 1

1000 2000 3000 4000 5000 1366.61 1721.77 2075.94 2253.02 2607.19 2962.34 3316.49 3670.64 4024.78 4379.91 m/z

Figure S33 MALDI-ToF mass spectrum(DCTB, NaTFA) of Polymer 2

2604 2605 2606 2607 2608 2609 2610 2611 2612 2613 2614 2615 2593.16 2594.18_2595.17 2596.16 2597.16 2606.19 2607.19 2608.18 2609.18 2610.2 2611.2 m/z 2780 2782 2784 2786 2788 2790 2792 2783.25 2784.25 2785.26 2786.26 2787.26 2788.26 m/z

2000 3000 4000 5000 6000 1394.62 1749.79 2103.95 2635.18 3167.44 3344.51 3698.68 4052.81 4407.93 4939.12 5470.27 6002.34 4463.18 m/z

Figure S34 MALDI-ToF mass spectrum(DCTB, NaTFA) of Polymer 3

Figure S35 MALDI-ToF mass spectrum(DCTB, NaTFA) of Polymer 4

2632 2634 2636 2638 2640 2634.18 2635.18 2636.19 2637.19 2638.22 2639.192640.19 m/z 3297 3298 3299 3300 3301 3302 3303 3304 3305 3306 3307 3308 3299.61 3300.58 3301.59 3302.59 3303.6 3304.6 3305.6 _3318.55 m/z

2000 4000 6000 8000 1529.61 1883.76 2415 2947.26 3478.56 4009.8 5428.44 6136.75 6844.98 7554.14 m/z 4542.06 4896.21

Figure S36 MALDI-ToF mass spectrum(DCTB, NaTFA) of Polymer 5

2000 4000 6000 1352.63 1706.8 1883.9 2238.06 2415.18 2770.36 3124.55 3655.82 4010.03 4365.23 4719.4 5073.57 5427.72 5782.87 6314.07 6845.27 m/z

Figure S37 MALDI-ToF mass spectrum(DCTB, NaTFA) of Polymer 6

4538 4540 4542 4544 4546 4548 4540.08 4541.05 4542.06 4543.06 4544.07 4545.07 m/z 4539.03 4360 4362 4364 4366 4368 4370 4372 4363.26 4364.21 4365.23 4366.21 4367.23 4368.25 m/z 4362.18

2000 3000 4000 1217.59 1571.75 1926.932104.01 2458.18 2812.35 3167.5 3521.66 3875.83 m/z

Figure S38 MALDI-ToF mass spectrum(DCTB, NaTFA) of Polymer 7

2000 4000 6000 1772.82 2020.08 2514.582762.78 3257.16 3751.51 4246.83 4494.01 5482.63 6225.06 6719.32 m/z 4988.28

Figure S39 MALDI-ToF mass spectrum(DCTB, NaTFA) of Polymer 8

2102 2104 2106 2108 2103.02 2104.01 2105.02 2106.01 m/z 2107.03 4492 4496 4500 4492.01 4493.01 4494.01 4495.01 4496.08 m/z 4490.98 4497.01

1500 2000 2500 3000 1363.54 1542.59 1722.66 1901.72 2259.86 2617.98 2976.12 m/z

Figure S40 MALDI-ToF mass spectrum(DCTB, NaTFA) of Polymer 9

1900 1902 1904 1906 1900.71 1901.72 1902.72 1903.73 m/z 1904.69

Figure S41 MALDI-ToF mass spectrum(DCTB, AgTFA) of Polymer 10

2320 2322 2324 2326 2328 2321.059 2322.048 2323.062 2325.067 2326.057 m/z 2392 2394 2396 2398 2400 2402 2394.037 2395.042 2396.047_2397.027 2398.033 2399.039 m/z 2334 2336 2338 2340 2342 2344 2336.02 2337.038 2338.03_2339.023 2340.041 2341.035 2342.028 m/z N O O Ph 12 Ag Mmonoisotopic = 2335.92

1500

2000

2500

3000

3500

1333.506

1510.596

1687.693

1791.784

1968.869

2041.86

2323.062

2396.047

2500.133

2678.222

2855.315

3032.405

3105.371

3209.48

3386.569

3563.64

m/z

Figure S42 MALDI-ToF mass spectrum(DCTB) of Polymer 11

4184 4186 4188 4190 4192 4194 4185.203 4186.2 4187.23 4188.228 4189.225 4190.223 4191.22 m/z 4258 4260 4262 4264 4266 4258.233 4259.172 4260.178 4261.184 4262.19 4263.196 m/z 4198 4200 4202 4204 4206 4208 4199.339 4200.171 4201.17 4202.2024203.201 4204.201 4205.2 4206.299 4207.166 4208.332 4210.298 m/z N O O Ph 23 Na Mmonoisotopic = 4199.87 2500 3000 3500 4000 4500 5000 5500 6000 6500 2946.642 3301.818 3655.978 4187.23 4542.373 5073.625 5427.843 5960.083

m/z

Figure S43 MALDI-ToF mass spectrum(DCTB) of Polymer 12

7726 7728 7730 7732 7734 7736 7738 7728.822 7729.816 7730.81 m/z 7727.829 7731.804 7732.798 7733.701 7734.695 7735.690 7798 7800 7802 7804 7806 7808 7810 7801.805 7802.804 7803.802 7805.709 m/z 7804.801 7806.707 7807.706 7800.807 7742 7744 7746 7748 7750 7752 7743.735 7744.73 7746.719 7747.714 m/z 7745.725 7742.831 7748.756 7749.652 7750.677 N O O Ph 43 Na Mmonoisotopic = 7741.45 6000 8000 10000

6313.201

6845.408

7376.644

7730.81

8085.893

8617.157

9149.309

m/z

Figure S44 1_{H-NMR spectrum(300 MHz, CDCl}

3) of Polymer 10

The polymer end groups corresponding to both, the vinyl acetate (a) as well as the tert.-butyl ether (b) are marked in the spectrum. The inset shows the terminating agent 4.

20.0 20.5 21.0 21.5 22.0 22.5 23.0 23.5 24.0 Retention Volume (ml)

6800 g/mol 5400 g/mol 3900 g/mol

Figure S45 GPC (THF, polystyrene as standards, RI detector) of different molecular weight of poly(MNI)-Ot-Bu

Figure S46 GPC (THF, polystyrene as standards, RI detector) of different molecular weight of poly(MNI)-Ot-Bu

with G1. “■” = Mn (g/mol) and “▲” = Mw/Mn.

Figure S47 GPC (Chloroform, polystyrene as standard, RI detector) of different molecular weight of poly(MNI)-Ot-Bu with G3. “●” = Mn (g/mol) and “●” = Mw/Mn.

References

(1) Bai, Y.; Xing, H.; Lu, Y.; et. al. ACS Nano 2015, 9, 10227;

(2) Hillmyer, M. A.; Grubbs, R. H.; et. al. Macromolecules 1992, 25, 3345.

10

20

30

4000

5000

6000

7000

1.0

1.5

2.0

Mn

M

w/M

n

10

20

30

2000

4000

6000

8000

10000

12000

1.0

1.5

2.0

Mn

M

w/M

n