S1

Supporting Information

Substituted Tris(2-pyridylmethyl)amine Ligands for Highly Active ATRP

Catalysts

Kristin Schröder, Robert T. Mathers, Johannes Buback, Dominik Konkolewicz, Andrew J. D. Magenau, and Krzysztof Matyjaszewski*

Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, USA

S2

General:

Materials. All chemicals were purchased from commercial sources, e.g., Aldrich, TCI, and used

as received if not stated otherwise. Tris(2-pyridylmethyl) amine (TPMA) was purchased from

ATRP Solutions. Methyl acrylate (MA) and butyl acrylate (BA) were passed through a column

filled with basic alumina to remove inhibitor prior to use. All manipulations for atom transfer

radical polymerizations were performed with oxygen free solvents, degassed by at least three

Freeze-Pump-Thaw cycles (FPT), using standard Schlenk techniques.

Instrumentation.

Gel permeation chromatography (GPC): GPC was used to determine number average

molecular weight (Mn) and Mw/Mn values. The GPC was conducted with a Waters 515 HPLC

Pump and Waters 2414 Refractive Index Detector using PSS columns (Styrogel 102, 103, 105 Å)

in tetrahydrofuran (THF) as an eluent at a flow rate of 1 mL/min at 35 oC. The column system

was calibrated with 12 linear polystyrene (PSt, Mn = 376~2,570,000) and 12 linear poly(methyl

methacrylate) (PMMA, Mn = 800 ~ 2,570,000) standards. Conversion of monomer was

determined by 1H NMR spectroscopy or gravimetrically. Absolute values of PMA may be

calculated utilizing universal calibration as reported in literature.[1]

NMR: Monomer conversion was measured using 1H NMR spectroscopy, using a Bruker Avance

300 MHz or 500 MHz spectrometer at room temperature. For ligand synthesis, NMR spectra

were measured using spectrometers at 300 MHz (1H) and 75 MHz (13C). All spectra were

recorded in CDCl3 and chemical shifts (δ) are reported in ppm relative to tetramethylsilane

referenced to the residual solvent peaks.[2] Spectra were measured at room temperature unless

otherwise stated.

MS: Mass spectra were recorded on a mass spectrometer with a Varian Saturn 2100T MS with

3900 GC using an EI source. In each case, characteristic fragments with their relative intensities

in percentages are shown. Electrospray mass spectra were measured on a Thermo-Fisher LCQ

ESI/APCI Ion Trap containing a quadrupole field ion trap mass spectrometer with electrospray

ionization (ESI).

CV: All cyclic voltammograms (CV) were measured at 25 o C with a PARC 263A potentiostat.

Solutions of CuBr2/TPMA* and Cu(OTf)2/TPMA* (1.0/1.0 mM) were prepared in dry solvent

containing 0.1 M NBu4PF6 as the supporting electrolyte. Measurements were carried out under a

N2 atmosphere at a scanning rate () of 0.1 V s-1, using a glassy carbon disk and platinum mesh

S3

as the working and counter electrode, respectively. Potentials were measured versus a SCE

reference electrode (Gamry) equipped with a 0.1 M NBu4PF6 salt bridge to minimize Cl- ion

contamination of the analyte.

Stopped-flow measurements: [CuI] decrease and [CuII] increase was followed with a stopped-

flow apparatus consisting of a BioLogic Science Instruments MOS450 monochromator, equipped

with a 150W Xe lamp and a photomultiplier 400, and a SFM20 stopped-flow module, equipped

with two 10 mL gastight Hamilton syringes. Data acquisition and analysis was done with Bio-

Kine 4.2. All kinetics were measured at 25°C in degassed acetonitrile in a FC15 cuvette with an

optical path length of 1.5 mm. [CuI] decrease superposed by [CuII] increase was followed at 405

nm and [CuII] increase alone was followed at 800 nm. For quantitative analysis the data at 405

nm was used due to a higher signal-to-noise ratio. The dead time was determined by conventional

methods to be 5.3 ms. For every measurement a total volume of at least 0.24 mL was pushed

through the cuvette with a flow-rate of 7 mL/s.

For the determination of KATRP, one 20 mM stock solution of CuBr (28.7 mg in 10 mL

acetonitrile), one 23 mM stock solution of TPMA* (97 mg in 10 mL acetonitrile) and one 20 mM

stock solution of methyl 2-bromopropionate (33.4 mg in 10 mL acetonitrile) were prepared. The

first syringe of the SFM 20 contained a 2 mM solution of CuI/TPMA*, prepared by adding 1 mL

of the respective stock solutions to 8 mL acetonitrile, and the second syringe contained a 2 mM

methyl 2-bromopropionate (MBP) solution prepared by adding 1 mL of the MBP stock solution

to 9 mL of acetonitrile.

Additionally, for the ka measurements a 20 mM MBP and 20 mM 2,2,6,6-tetramethylpiperidinyl-

1-oxy (TEMPO) solution in acetonitrile (31.25 mg TEMPO) and a solution containing only 20

mM TEMPO were prepared. The first syringe contained the same 2 mM solution of CuI/TPMA*

as in the KATRP measurements. The second syringe was filled either with the 20 mM solution of

MBP and TEMPO or with the 20 mM solution of TEMPO alone.

All solutions and syringes were degassed by repetitive FPT cycles before and after addition of the

respective compound.

Additional Results:

Ligand Synthesis:

S4

N

OMe

Cl

DMF, K2CO3, 85°C, N2N

OMe

N

O

O

N

OMe

NH2

Me Me Me

Me Me

Me

.HCl

N

Cl.HCl

N

N

NNN2, Na2CO3, CH3CN

OMe

MeMeMeO

Me

Me

OMe

Me

Me

OMe

Me Me

TPMA*

EtOH/toluene 2:1,reflux, N2

H2NNH2

41%

73%

quantitative

N

O

O

K

SI Scheme 1. Synthesis route for TPMA*.

Synthesis of TPMA*: 2-Phthalimidomethyl-4-methoxy-3,5-dimethylpyridine. 4.88 g 2-

chlormethyl-4-methoxy-3,5-dimethylpyridine hydrochloride (21.9 mmol) was dissolved in 75 mL

anhydrous DMF. 4.05 g phthalimide potassium salt (21.9 mmol) was added and the solution was

stirred for 5 minutes. After the addition of 12.67g K2CO3, the mixture was heated under nitrogen

at 85 °C for 19 h and followed by GC-MS. Then the solution was allowed to cool to r.t. and a

white solid precipitated when adding saturated NaHCO3. The off white solid was filtered,

resolved in CH2Cl2, dried over MgSO4 and concentrated in vacuum to give 4.75 g (= 73%) of a

white solid (pure product). Analytical data is in accordance with previous literature.[3] 1H NMR

(300 MHz, CD3Cl): δ (ppm) = 8.047 (s, 1H), 7.883 (dd, J= 3.1 Hz, J’=5.5 Hz, 2H), 7.722 (dd, J=

3.1 Hz, J’=5.5 Hz, 2H), 4.920 (s, 2H), 3.752 (s, 3H), 2.319 (s, 3H), 2.175 (s, 3H); 13C NMR (75

MHz, CD3Cl): δ (ppm) = 168.70, 163.90, 152.30, 149.48, 133.94, 132.70, 125.17, 123.53, 60.09,

40.75, 13.31, 10.63; MS (EI): m/z (rel. int.): 298.1 (18), 297.1 (100), 296.3 (22).

2-Aminomethyl-4-methoxy-3,5-dimethylpyridine. Anhydrous hydrazine (932.8 mg, 30.54

mmol) was added to a stirred solution of 2-phthalimidomethyl-4-methoxy-3,5-dimethylpyridine

(1.51 g, 5.099 mmol) in 50 mL (anhydrous: EtOH/toluene=2/1) under N2. The mixture was

heated to 85 °C for 24 h during which time a white precipitate was formed. After cooling to room

temperature the remaining solvent was removed under high vacuum and the residue was

dissolved in 46 mL of 40% KOH. After extraction with CH2Cl2 the product was dried with

MgSO4 to give a quantitative yield, 845 mg, of a pale yellow oil, which was confirmed to be pure

S5

by GC-MS (EI). Then the product was reacted directly with 2-chloromethyl-4-methoxy-3,5-

dimethylpyridine hydrochloride. MS (EI): m/z (rel. int.): 167(100), 166(52), 165(16), 151(48),

149(41), 138(22), 136(10), 123(14), 122(25), 121(16), 120(10), 119(17), 107(13), 106(16),

94(14), 92(14), 77(12).

(Tris[{(4-methoxy-2,5-dimethyl)-2-pyridyl}methyl]amine (TPMA*). 2.66 g of the amine

(0.016 mol) and 7.125 g of the chloride (0.0321 mol) and 8.5 g of Na2CO3 were weighed into a

two necked flask and dissolved in 300 mL HPLC grade acetonitrile. Then 3 mg of TBABr was

added to the stirred solution under nitrogen. The mixture was heated to reflux (T = 82 °C) under

nitrogen for 48 h and the reaction was followed by mass spectroscopy and TLC. The mixture

was allowed to cool to r.t. and poured into 150 mL 1 M NaOH. After extraction with CH2Cl2 (3

times), the combined organic fractions were dried over MgSO4, filtered and the solvent was

evaporated under reduced pressure to give an orange/brown crude product (m=6.177g).

Purification over alumina (MeOH:EtOAc=5:95) gave 3.06 g (= 41 %) of a pure yellowish solid.

Analytical data is in accordance with previous literature.[4] Rf: 0.45 (MeOH:EtOAc 95:5); 1H

NMR (300 MHz, CD3Cl): δ (ppm) = 8.187 (s, 3H), 3.746 (s, 6H), 3.659 (s, 9H), 2.228 (s, 9H),

1.613 (s, 9H); MS (ESI) m/z: 465.3 (M+H)+.

S6

Catalyst Characterization:

CV:

-0.8 -0.6 -0.4 -0.2 0.0 0.2-20

-15

-10

-5

0

5

10

15 CuIITrf/TPMA* (E

1/2 = -0.150 V)

CuIIBr/TPMA* (E

1/2 = -0.420 V)

I (A

)

E (V vs SCE)

[Cu/L] = [Br] = 1 mM

= 190, = 100 mv/s

-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4

-200

-150

-100

-50

0

CuIIBr/L CuIIBr/L + EBiB

I (A

)

E (V vs SCE)

(B)

SI Figure 1. Cyclic voltammetry of (A) CuII/TPMA* in the absence (dashed line) and presence

(solid line) of bromide anions, and of (B) CuIIBr/TPMA* in the absence (dashed line) and

presence (solid line) of an alkyl halide. All cyclic voltammetry measurements were conducted in

MeCN with 0.1 M TBAPF6 supporting electrolyte at a scan rate of 100 mV/s at T = 25 °C. The

following concentration were used: [CuII(OTf)2] = 1 mM, [TPMA*] = 1 mM, [TBABr] = 1 mM,

and [EBiB] = 10 mM.

Stopped-flow:

KATRP Results:

(A) (B) SI Figure 2. (A) Time-resolved [CuII] increase measured at 405 nm, [Cu/TPMA*]0 =1 mM,

[MBP]0 =1 mM. (B) Blue: experimental data converted to F(Y) of Tang et al.[5]; red: linear fit

starting at t=3 s to the experimental data.

S7

Conclusion: With the slope m=1212.4 M-1 s-1, values of kt = 3.5 x 109 M-1 s-1: KATRP = (m/2kt)

1/2=4.2 x 10-4 were calculated.

ka Results:

(A) (B) SI Figure 3. Time resolved [CuI] to [CuII] conversion ([Cu/TPMA]0 =1 mM) due to activation of

MBP (10 mM) and trapping of the generated radicals with TEMPO (10 mM) at 390 nm (A) and

405 nm (B). Blue: experimental data; red: mono-exponential fit to the experimental data.

Conclusion: Pseudo-first-order kinetics were generated with a ten-fold excess of initiator (10

mM) versus Cu/TPMA* (1 mM) in acetonitrile. The ten-fold excess is a compromise between

reaction speed and amplitude of the signal decrease, since a 20-fold excess would lead to the

lifetime of the decrease being shorter than the dead time of the stopped-flow apparatus (5.3 ms).

The data at 390 nm and 405 nm show different amplitudes but almost the same rate constant of

82 s-1 and 86 s-1, respectively. Dividing this rate constant by [MBP]0 = 10 mM, a second order

rate constants ka = 8200 s-1M-1 and ka = 8600 s-1M-1 (arithmetic average: ka = 8400 s-1M-1) were

calculated. No shifting of the Abs scale has been performed, as the amplitude and the offset of

the exponential decay was not of interest for the analysis.

S8

SI Figure 4. Time resolved [CuI] to [CuII] conversion; without initiator MBP no dynamics can be

observed at all (the same experimental conditions as in Figure 3).

Polymerizations Studies:

Polymerization Procedures:

Normal ATRP. [MA]: [EBP]: [CuIBr]: [TPMA*]: = [232]:[1]:[0.2]:[0.2]. MA (4.184 g, 0.0486

mol), ethyl 2-bromopropinate (EBP) (37.9 mg, 2.095 x 10-4 mol) and TPMA* (19.5 mg, 4.19 x

10-5 mol) were dissolved in the monomer and charged into a 10 mL Schlenk flask. The reaction

mixture was degassed by at least three FPT cycles and filled with nitrogen again. CuBr (6.0 mg,

4.19 x 10-5 mol) was added to another 10 mL Schlenk flask equipped with a stir bar. The flask

was evacuated and refilled with nitrogen at least 3 times over a period of 20 min. The monomer

mixture was then transferred under nitrogen via gas-tight syringe to the CuBr Schlenk flask and

the flask was placed in an oil bath at T= 30°C to start the reaction.

ARGET ATRP. [BA]:[EBiB]:[Sn(EH)2]:[TPMA*]:[CuCl2]= [160]:[1]:[0.1]:[0.03-0.06]: [0.008-

0.016] BA (3.768 g, 0.0294 mol), ethyl 2-bromoisobutyrate (EBiB) (35.8 mg, 1.8375 x 10-4 mol)

and stock solutions of CuCl2 in DMF and TPMA* in anisole were dissolved in anisole ( 20%

(v/v)) and charged into a 10 mL Schlenk flask equipped with a stir bar. The reaction mixture was

degassed by at least three FPT cycles, purged with nitrogen again and placed in an oil bath. A

degassed stock solution of Sn(EH)2 in anisole, purged with nitrogen for at least 20 min, was

added to the reaction solution to activate the catalyst complex and start the reaction.

S9

SARA ATRP. A length of Cu0 wire (16 cm) with a 1 mm diameter was washed with HCl/MeOH

(20 % v/v) for 10 min, rinsed with MeOH, and dried. A stir bar, ligand (0.1 equiv, 0.018 mmol),

and the Cu0 wire were added to a Schlenk flask and purged with nitrogen. After bubbling a

solution of methyl 2-bromopropionate (MBP) in DMSO for 1 h, an aliquot of the solution (1.68

mL) containing MBP (1.0 equiv, 0.18 mmol) was added to the Schlenk flask via syringe. Then,

methyl acrylate (MA) (200 equiv, 36.0 mmol), that had been filtered through a short column of

basic alumina (Al2O3) and bubbled with nitrogen for 1 h, was quickly added. The MA

polymerization in DMSO (33.3 % v/v) proceeded at 25° C in a water bath.

eATRP. [BA]/[EBiB]/[TPMA*]/[CuII(OTf)2]/[TBABr] = 300/1/0.03/0.03/0.03. Controlled-

potential electrolysis experiments were carried out with a PARC 263A potentiostat in a

thermostated three-electrode cell using both platinum (Pt) disk (3 mm diameter, Gamry) and Pt

gauze (100 mesh, geometrical area ~2.5 cm2, Alfa Aesar) working electrodes. An Ag/AgI/I−[6]

and Pt mesh were used as the reference and counter electrodes, respectively. The electrolysis

experiments were carried out in a divided cell, using a glass frit and a salt bridge made of

methylcellulose gel saturated with Et4NBF4 to separate the cathodic and anodic compartments.

All experiments were performed at 25 °C. During electrolysis, the cathodic compartment was

maintained under vigorous magnetic stirring and an N2 atmosphere. Prior to each experiment, the

working Pt disk electrode was polished with a 0.25-μm diamond paste and sonicated in ethanol.

The electrochemical cell was first charged with supporting electrolyte (1.603 g TBAClO4) and

then put under a slow N2 flow. After 15 minutes of purging, 13 mL of BA, 10 mL of DMF, 0.18

mL of a 0.05 M solution of CuII/TPMA*/TBABr (equimolar), and 45 μL of neat EBiB were

added to the electrochemical cell. Samples were withdrawn periodically for 1H NMR and GPC

analysis for conversion, and molecular weight and distribution determination, respectively.

ICAR ATRP. [BA]:[EBiB]:[AIBN]:[TPMA*]:[CuCl2] =[160]:[1]:[0.2]:[0.0016-0.016]: [0.006-

0.06]. BA (3.21 g, 0.025 mol), ethyl 2-bromoisobutyrate (EBiB) (30.5 mg, 1.565 x 10-4 mol),

AIBN (5.1 mg, 3.13 x 10-3 mol) and stock solutions of CuCl2 in DMF and TPMA* in anisole

were dissolved in anisole (Vtot = 0.715 mL; 20% (v/v)) and charged into a 10 mL Schlenk flask

equipped with a stir bar. The reaction mixture was degassed by at least three freeze-pump-thaw

cycles and purged with nitrogen again. Then the mixture was placed in an oil bath (T = 60°C) to

start the polymerization

S10

SI Table 1. Results for bulk ATRP under the following conditions : [MA]: [EBP]: [CuIBr]:

[TPMA*]: = [232]:[1]:[0.2]:[0.2] ; [MA]=10.8 M; T= 30 °C.

Time

[h]

Conv.(NMR)

[%] Mn,GPC Mn,theo Mw/Mn DP,theo DP,exp

0.25 4.7 1820 1124 1.35 11 21

0.5 5.1 2070 1208 1.36 12 24

0.75 6.8 2210 1543 1.34 16 26

1 7.2 2380 1625 1.34 17 28

1.5 9.8 2560 2134 1.28 23 30

2 9.8 2790 2136 1.23 23 32

3 11.1 3030 2390 1.27 26 35

5.15 13.5 3220 2885 1.25 31 37

103 104

1h // 13.3% // 3680 // 1.69

molecular weight

time // conversion // Mn // M

w/M

n

2h // 19.4% // 4800 // 1.54

50 ppm CuT= 60 °Creduced Sn(EH)

2

3h // 24.5% // 5910 // 1.45

5h10m // 32.4% // 5970 // 1.39 7h // 38.2% // 7330 // 1.34 21h // 71.9% // 16300 // 1.16

(A)

0 5 10 15 200

20

40

60

80

100

con

vers

ion

(%

)

time (h)

0.0

0.5

1.0

1.5

ln

([M

] 0/[

M])

(C)

0 10 20 30 40 50 60 70 80 90 1000

5

10

15

20

Mn x

10

-3

conversion (%)

1.0

1.5

2.0

2.5

Mw/M

n

(B)

S11

SI Figure 5. ARGET ATRP of BA with 50 ppm and 0.05 equiv Sn(EH)2, (A) GPC traces, (B)

Mw/Mn and Mn as function of conversion, and (C) first order kinetic plots (Table 1, entry 6).

0.0 0.5 1.0 1.5 2.0 2.50.0

0.5

1.0

1.5

TPMA TPMA*

ln (

[M] 0

/[M

])

time (h)

(A)

0 20 40 60 800

5

10

15

20

25

30

35

Mn x

10

-3conversion (%)

(B)M

n,theo

1.10

1.15

1.20

1.25

1.30

1.35

1.40

Mw/M

n

SI Figure 6. eATRP for TPMA and TPMA*: (A) First order kinetic plot and (B) Mn and Mw/Mn

as function of conversion under the following conditions:

[BA]/[EBiB]/[TPMA*]/[CuII(OTf)2]/[TBABr] = 300/1/0.03/0.03/0.03, [BA] = 3.9 M,

[TBAClO4] = 0.2 M, and T = 25 °C.

0 1 2 3 4 5-2.0

-1.6

-1.2

-0.8

-0.4

0.0

Cu

rre

nt

(mA

)

time (h)

TPMA* TPMA

SI Figure 7. Current versus time profile of eATRP (conditions as in Figure 6).

S12

SI Figure 8. GPC trace for ICAR ATRP with 50 ppm catalyst loading.

SI Table 2. ICAR ATRP of n-butyl acrylate.

Entry[a]

Catalyst

loading

[ppm]

Conv.

[%]

Time

[h]

Mn,theo[c]

Mn,GPC Mw/Mn DP,theo DP,exp

1 5 92.8 3 22900 19200 1.43 148 179

2[b] 5 88.9 3 27000 18400 1.90 142 211

3 10 81.7 3 16900 15900 1.47 131 124

4[b] 10 86.1 3 17900 27300 3.07 138 236

5 20 90.8 4 18800 18400 1.28 145 143

6 50 82.8 4 17200 17400 1.17 132 136

7[b] 50 38.0 4 8000 8230 1.67 61 64

8 100 67.9 4 14100 13200 1.15 109 103

[a] [BA]:[EBiB]:[AIBN]:[TPMA*]:[CuCl2] =[160]:[1]:[0.2]:[0.006-0.06]:[0.0016-0.016], [BA]=5.88 M, 20% (v/v) anisole, the Cu :TPMA* = 1:3.75 ratio was held constant, conversion was determined by 1H-NMR, T= 60 °C ; [b] TPMA was used instead of TPMA*; [c] Mn,theo = [M]/[I] x conv. x MMonomer+MInitiator.

S13

0 20 40 60 80 1000

10

20

30

40 Cu/TPMA* Cu/TPMA Mn,theo

Mn x

10

-3

conversion (%)

(A)

1.5

2.0

2.5

3.0

3.5

Mw/M

n

SI Figure 9. ICAR ATRP of BA with 5 ppm of catalyst loading (Table 2, entries 1-2): (A) Mw/Mn

and Mn as function of conversion, and (B) pseudo-first order kinetic plots.

Kinetic Modelling:

0.0 0.2 0.4 0.60.0

0.2

0.4

0.6

0.8

1.0

CuI

I :Cu

Tot

conversion (%)

Cu/TPMA* Cu/TPMA

(A)

0.0 0.5 1.0 1.5 2.0 2.5 3.00

1

2

Ln

([M

] 0/[M

])

time (h)

(B)

SI Figure 10. PREDICI® simulations for normal ATRP: (A) ratio CuII /CuTot vs conversion; (B)

semilogarithmic plot vs time under the following conditions: [MA]:[MBP]:[CuI]:[CuIIBr]=

200:1:0.2:0, [MA]= 5.5 M, 50 % (v/v) MeCN, T=25 °C.

0 1 2 30

20

40

60

80

100

co

nv

ers

ion

(%

)

time (h)

Cu/TPMA* Cu/TPMA

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Linear Fit R2 = 0.995

ln

([M

] 0/[

M])

Cu/TPMA*: kapp = 0.817 hr-1

(B)

S14

0.0 0.5 1.0 1.5 2.0 2.50

1

2 Cu/TPMA* Cu/TPMA

Ln

([M

0]/[M

])

time (h)

(A)

0.0 0.2 0.4 0.6 0.80.0

0.5

1.0

Cu

II/C

uto

t

conversion (%)

(C)

SI Figure 11. PREDICI® simulations for ICAR ATRP with 50 ppm catalyst: (A) semilogarithmic

plot vs time ; (B) Mw/Mn vs conversion and (C) : ratio CuII /CuTot vs conversion under the

following conditions: [MA]:[MBP]:[V-70]:[CuI]:[CuIIBr]= 200:1:0.2:0:0.01 (50 ppm Cu), [MA]=

5.5 M, 50 % (v/v) MeCN, T=25 °C.

PREDICI® Simulations:

General: PREDICI® (v 6.3.2) was used for all simulations.

In all simulations of normal ATRP and ICAR ATRP reactions the polymerization of methyl

acrylate (MA) at 25 °C were simulated. The following abbreviations are used: Monomer (M),

initiator (RBr), 2,2'-azobis(4-methoxy-2.4-dimethyl valeronitrile) (V-70), azobisisobutyronitrile

(AIBN), isobutyronitrile (IBN), tris[2-(dimethylamino)ethyl]amine (Me6TREN). The rate

coefficients used in the simulations are presented in Table 3. The activation and deactivation rate

coefficients for TPMA and TPMA* are given in Table 4. These rate coefficients are based on

0.0 0.2 0.4 0.6 0.81.0

1.2

1.4

1.6

1.8

2.0

Mw

/Mn

conversion (%)

(B)

S15

previous published results by our group[5] and experimental obtained data from previously

described stopped-flow measurements.

SI Table 3. The rate coefficients for the intrinsic radical reactions for MA with/and V-70

initiators at 25 oC.

Rate coefficient Value kp (MA) 15600 M-1 s-1 [7] kp,I (MA) 245 M-1 s-1 [7-8] kt0 (MA) 1 109 M-1 s-1 [9] kt (MA) 1 108 M-1 s-1 [10]

kazo (V-70) 8.9 10-6 s-1 [11]

SI Table 4: The rate coefficients for the ATRP activation deactivation processes for Cu/TPMA

and Cu/TPMA* catalysts with methyl 2-bromopropionate (MBrP) as initiator at 22 oC. No

additional scaling was performed for the temperature difference to 25 oC.

Catalyst ka (M-1 s-1) kda (M

-1 s-1)

TPMA 3.8 100 1.2 107

TPMA* 8.4 103 1.7 107

Normal ATRP: The initial conditions were the following: [M]:[RX]:[CuI]:[CuIIBr]= 200:1:0.2:0

SI Table 5. Reaction scheme for normal ATRP, assuming that the initiator and the

macromolecular species have the same reactivity.

RBr + CuBr ka

R + CuBr2 (1)

R + CuBr2 kd

RBr + CuBr (2)

R + M kp,I

P (1) (3)

P(j) + M kp

P(j+1) (4)

P(j) + CuBr2 kd

P(j)X + CuBr (5)

P(j)X + CuBr ka

P(j) + CuBr2 (6)

R + R kt0

D (7)

P(j) + R kt0

D(j) (8)

S16

P(j) + P(k) kt

D(j+k) (9)

ICAR ATRP: The initial conditions were the following: [M]:[RBr]:[V-70]:[CuI]:[CuIIX]=

200:1:0.2:0:0.01 (50 ppm Cu). Initiator V-70 was chosen due to its relatively fast rate of initiator

dissociation at 25 °C. The initiation efficiency of the azo initiator, was assumed to be 50%.

SI Table 6. Reaction scheme for ICAR ATRP, assuming the initiator and macromolecular species

have the same reactivity, but the azo fragment has higher reactivity.

I2 kazo

I (10)

IX + CuBr ka,I

I + CuBr2 (11)

I + CuBr2 kd,I

IBr + CuBr (12)

I + M kp

P (1) (13)

RBr + CuBr ka

R + CuBr2 (14)

R + CuBr2 kd

RBr + CuBr (15)

R + M kp,I

P (1) (16)

P(j) + M kp

P(j+1) (17)

P(j) + CuBr2 kd

P(j)X + CuBr (18)

P(j)Br + CuBr ka

P(j) + CuBr2 (19)

R + R kt0

D (20)

P(j) + R kt0

D(j) (21)

R + I kt0

D (22)

I + I kt0

D (23)

P(j) + I kt0

D(j) (24)

P(j) + P(k) kt

D(j+k) (25)

The activation/deactivation rate coefficients for the azo initiator fragment are determined by a

series of scaling calculations. The original data for AIBN and TPMA were measured in 2010,[12]

and the reactivity of the IBN radical and the V-70 fragment were assumed to be the same. The

activation rate constants were scaled from 5.8 104 M-1 s-1 to 1.8 104 M-1 s-1 using the

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activation energy of 28.1 kJmol-1 for bromopropionitrile (BrPN) as initiator.[13] This accounts for

the fact that a temperature of 60 oC was used to measure the IBN-Cl activation rate 5.8 104 M-1

s-1, and that the simulations are for a reaction temperature of 25 oC. KATRP was decreased by a

factor of 1.5, according to a previous protocol.[14]. Thus the reactivity of IBN-Cl at 25 °C is

obtained. Next the reactivity of the chloro group was converted to that of the bromo group. In this

case kd was assumed to be constant, whereas ka was rescaled by the ratio 50 according to

literature data. [5] Finally the solvent effect (factor of 0.8) was accounted according to previous

published data [15] as the data for AIBN was determined in MeOH instead of MeCN. In this case

the solvent effect was assumed to purely affect the ka. Thus, ka and kd for IBN-Br with TPMA are

obtained. According to the previously published data, the reactivity TPMA and Me6TREN were

almost the same with IBN-Cl. Therefore the reactivity for TPMA* was taken to be the same as

for TPMA.

SI Table 7. The rate coefficients for the ATRP activation deactivation processes for various

catalysts with IBN-Br at 25 °C.

Catalyst ka,I (M-1 s-1) kd,I (M

-1 s-1)

TPMA 7.2105 2.6107

TPMA* 7.2105 2.6107

References:

[1] T. Gruendling, T. Junkers, M. Guilhaus, C. Barner-Kowollik, Macromol. Chem. Phys.

2010, 211, 520-528. [2] H. E. Gottlieb, V. Kotlyar, A. Nudelman, J. Org. Chem. 1997, 62, 7512-7515. [3] R. D. Rasberry, M. D. Smith, K. D. Shimizu, Org. Lett. 2008, 10, 2889-2892. [4] G. Xue, D. Wang, R. De Hont, A. T. Fiedler, X. Shan, E. Münck, L. Que, PNAS 2007,

104, 20713-20718. [5] W. Tang, Y. Kwak, W. Braunecker, N. V. Tsarevsky, M. L. Coote, K. Matyjaszewski, J.

Am. Chem. Soc. 2008, 130, 10702-10713. [6] A. A. Isse, G. Sandonà, C. Durante, A. Gennaro, Electrochim. Acta 2009, 54, 3235-3243. [7] M. Buback, C. H. Kurz, C. Schmaltz, Macromol. Chem. Phys. 1998, 199, 1721-1727. [8] J. P. A. Heuts, G. T. Russell, Eur. Polym. J. 2006, 42, 3-20. [9] G. B. Smith, G. T. Russell, J. P. A. Heuts, Macromol. Theor. Simul. 2003, 12, 299-314. [10] G. Johnston-Hall, M. J. Monteiro, J. Polym. Sci. A: Polym. Chem. 2008, 46, 3155-3173.

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[11] K. W. Dixon, in Polymer Handbook, Fourth ed. (Eds.: J. Brandrup, E. H. Immergut, E. A. Grulke), John Wiley and Sons, New York, 1999, p. II/8.

[12] M. N. C. Balili, T. Pintauer, Inorg. Chem. 2010, 49, 5642-5649. [13] F. Seeliger, K. Matyjaszewski, Macromolecules 2009, 42, 6050-6055. [14] K. Matyjaszewski, W. Jakubowski, K. Min, W. Tang, J. Y. Huang, W. A. Braunecker, N.

V. Tsarevsky, PNAS 2006, 103, 15309-15314. [15] W. A. Braunecker, N. V. Tsarevsky, A. Gennaro, K. Matyjaszewski, Macromolecules

2009, 42, 6348-6360.