Supporting Information for

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1 Supporting Information for AmPhos Pd-Catalyzed Suzuki-Miyaura Catalyst-Transfer Condensation Polymerization: Narrower Dispersity by Mixing the Catalyst and Base Prior to Polymerization Kentaro Kosaka, Tatsuya Uchida, Koichiro Mikami, Yoshihiro Ohta, Tsutomu Yokozawa* * yokozt01@kanagawa-u.ac.jp Table of Contents 1. Measurements... S2 2. Materials... S2 3. Model reaction of 1 and 2 with various Pd catalysts... S3 4. Polymerization of 6 with an initiator generated in situ from AmPhos Pd G2 and 5. S3 5. Synthesis of (tolyl)pdamphos(br) 7... S4 6. Polymerization of 6a with initiator 7 by usual addition method... S5 7. Polymerization of 6 with initiator 7 by mixing 7 and base prior to polymerization. S6 8. Model reaction of 1 and 2 with AmPhos Pd G2 in the presence of CsF/18-crown S7 9. Block copolymerization of 6a and then 6b... S7 10. GPC profile of P3HT obtained by mixing tolyl(pt-bu 3 )PdBr and CsF prior to polymerization (Figure S1)......S8 11. NMR spectra (Figure S2-S10)... S9 12. Supporting References... S17 S1

2 1. Measurements 1 H, 13 C, and 31 P NMR spectra were obtained on JEOL ECA-600 spectrometers. The internal standard for 1 H NMR spectra in CDCl3 was tetramethylsilane (0.00 ppm), and the internal standard for 13 C NMR spectrum in CDCl3 was the midpoint of CDCl3 (77.0 ppm). 31 P NMR spectrum was calibrated to an external standard of H3PO4 (0.00 ppm). The Mn and Mw/Mn values of polymers were measured on a Tosoh HLC-8020 gel permeation chromatography (GPC) unit (eluent, THF; calibration, polystyrene standards) with two TSK-gel columns (2 Multipore HXL-M). MALDI- TOF mass spectra were recorded on a Shimadzu/Kratos AXIMA-CFR plus in the reflectron and linear ion modes by use of a laser (λ = 337 nm). trans-2-[3-(4-tert-butylphenyl)-2-methyl-2- propenylidene]malononitrile (DCTB) was used as the matrix for the MALDI-TOF mass measurements. ESI-MS experiment was performed using high-resolution JEOL Accu TOF-CS instrument. The conversion of 1 and 2, and the yield of 3 and 4 were determined by analytical GC performed on a Shimadzu GC-2010 plus gas chromatograph equipped with a Restek dimethypolylsiloxane fluid Rtx-1 column (15 m) and a flame ionization detector. 2. Materials Commercially available dehydrated tetrahydrofuran (THF, stabilizer-free, Kanto) and pentane (Kanto) were used as dry solvents. 2,5-Dibromo-thiophene (2), CsF, K3PO4, and XPhos Pd G3, tbuxphos Pd G3, tbubrettphos Pd G3, catacxium A Pd G3, P(Cy)3 Pd G3 and AmPhos Pd G2 were purchased from Aldrich Inc, and were used as received. 18-Crown-6 (TCI), 2-bromotoluene (TCI), 4-iodobenzonitrile (TCI), 2-bromo-5-phenylthiopene (TCI) (3), 2,5-diphenylthiophene (TCI) (4), and phenylboronic acid neopentylglycol ester (1) (Wako) were used as received. 2-Iodo- S2

3 3-hexylthiophene-5-boronic acid pinacol ester 6a, 1 2-bromo-9,9-bis(octyl)-9H-fluorenen-7- boronic acid pinacol ester 6b 2 and tolyl(pt-bu3)pdbr 3 were prepared according to the cited literature. 3. Model reaction of 1 and 2 with various Pd catalysts All glass apparatuses were dried prior to use. Addition of reagents into a reaction flask and withdrawing a small aliquot of the reaction mixture for analysis were carried out via a syringe from a three-way stopcock under a stream of nitrogen. A round-bottomed flask equipped with a three-way stopcock was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. Pd precatalyst ( mmol), K3PO g (2.20 mmol) and 18-crown g (6.74 mmol) were placed in the flask, and the atmosphere in the flask was replaced with argon. Into the flask was added a solution of 2,5-dibromothiophene g (0.51 mmol) and naphthalene g (0.79 mmol) as an internal standard in dry THF (3.0 ml) and distilled water (0.4 ml) were added via a syringe, and stirred at room temperature for 1 h. To the mixture was added a solution of phenylboronic acid neopentylglycol ester g (0.50 mmol) in dry THF (2.0 ml) was added via a syringe at room temperature. The reaction was allowed to proceed for 72 h followed by quenching with 6 M hydrochloric acid. The organic layer was extracted with CH2Cl2, and the solution was analyzed by GC. 4. Polymerization of 6 with an initiator generated in situ from AmPhos Pd G2 and 5 S3

4 All glass apparatus was dried prior to use. Addition of reagents to a reaction flask and withdrawal of a small aliquot of the reaction mixture for analysis were carried out via a syringe from a threeway stopcock under a stream of nitrogen. A round-bottomed flask equipped with a three-way stopcock was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. Pd Amphos precatalyst G g ( mmol), p-iodobenzonitrile g ( mmol), K3PO g (0.642 mmol), and 18-crown g (0.120 mmol) were placed in the flask, and the atmosphere in the flask was replaced with argon. Dry THF (7.0 ml) and distilled water (0.45 ml) were added to the flask via a syringe, and the mixture was degassed with argon and stirred at room temperature for 1 h. A solution of monomer 6a g (0.098 mmol) in dry THF (5.0 ml, degassed with argon) was added to the reaction mixture, via a cannula, and the reaction mixture was stirred at room temperature. After 24 h, 6 M hydrochloric acid was added, and the mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was dissolved in THF and the solution was added to methanol to precipitate the product ( g, 96%). Similarly polymerization of 6b afforded polymer ( g, 78%). 5. Synthesis of (tolyl)pdamphos(br) 7 All glass apparatus was dried prior to use. Addition of reagents to a reaction flask was carried out via a syringe from a three-way stopcock under a stream of nitrogen. Schlenk flask was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. Bis(AmPhos)Pd(0) g (0.099 mmol) was placed in the flask, and the atmosphere in the flask was replaced with argon. 2-Bromotoluene 0.7 ml (5.9 mmol, degassed with argon by freeze- S4

5 pump-thaw cycling) was added to the flask via a syringe, and the mixture was degassed with argon by freeze-pump-thaw cycle and stirred at 70 o C for 2 h. Dry pentane (10 ml, degassed with argon by freeze-pump-thaw cycle) was added to the flask via a syringe, and stirred at room temperature for 30 seconds. The mixture was stored at room temperature for 30 minutes. Precipitate was collected by suction filtration under a stream of nitrogen, washed with dry pentane (degassed with argon by freeze-pump-thaw cycle), and dried under reduced pressure to give 7 as a yellow powder ( g, 52%); 1 H NMR (600 MHz, CDCl3) δ 7.87 (s, 2 H), 7.38 (d, J = 5.8 Hz, 1 H), 6.79 (d, J = 7.2 Hz, 1 H), 6.70 (t, J = 7.0 Hz, 1 H), 6.64 (t, J = 7.2 Hz, 1 H), 6.57 (d, J = 8.2 Hz, 2 H), 2.95 (s, 6 H), 2.93 (s, 3 H), (m, 18 H); 13 C NMR (151 MHz, CDCl3) δ 150.9, 138.3, 142.9, (d, J = Hz), 129.0, (d, J = 23.1 Hz), 127.8, (d, J = 21.6 Hz), (d, J = 8.8 Hz), 40.0, 33.1, 28.7, 28.5; 31 P NMR (243 MHz, CDCl3) δ 59.44; HRMS (ESI) calcd for C23H35NPPd + [M-Br] , found Polymerization of 6a with initiator 7 by usual addition method All glass apparatus was dried prior to use. Addition of reagents to a reaction flask and withdrawal of a small aliquot of the reaction mixture for analysis were carried out via a syringe from a threeway stopcock under a stream of nitrogen. A round-bottomed flask equipped with a three-way stopcock was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. Monomer 6a g (0.081 mmol), K3PO g (0.32 mmol), and 18-crown g (0.97 mmol) were placed in the flask, and the atmosphere in the flask was replaced with argon. Dry THF (3.5 ml) and distilled water (0.35 ml) were added to the flask via a syringe, and the mixture was degassed with argon. This mixture was added to a solution of initiator S5

6 g (0.004 mmol, 5.0 mol%) in dry THF (6.0 ml, degassed with argon), via a cannula, and the reaction mixture was stirred at room temperature. After 24 h, 6 M hydrochloric acid was added, and the mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was dissolved in THF and the solution was added to methanol to precipitate the product. 7. Polymerization of 6 with initiator 7 by mixing 7 and base prior to polymerization All glass apparatus was dried prior to use. Addition of reagents to a reaction flask and withdrawal of a small aliquot of the reaction mixture for analysis were carried out via a syringe from a threeway stopcock under a stream of nitrogen. A round-bottomed flask equipped with a three-way stopcock was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. Initiator g ( mmol), CsF g (0.310 mmol), and 18-crown g (0.485 mmol) were placed in the flask, and the atmosphere in the flask was replaced with argon. Dry THF (6.0 ml) and distilled water (0.45 ml) were added to the flask via a syringe, and the mixture was degassed with argon and stirred at room temperature for 1 h. A solution of monomer 6a g (0.103 mmol) in dry THF (6.0 ml, degassed with argon) was added to the mixture of initiator, via a cannula, and the reaction mixture was stirred at room temperature. After 24 h, 6 M hydrochloric acid was added, and the mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was dissolved in THF and the solution was added to methanol to precipitate the product. S6

7 8. Model reaction of 1 and 2 with AmPhos Pd G2 in the presence of CsF/18-crown-6 All glass apparatuses were dried prior to use. Addition of reagents into a reaction flask and withdrawing a small aliquot of the reaction mixture for analysis were carried out via a syringe from a three-way stopcock under a stream of nitrogen. A round-bottomed flask equipped with a three-way stopcock was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. AmPhos Pd G mg ( mmol), CsF mg (0.225 mmol) and 18-crown mg (0.435 mmol) were placed in the flask, and the atmosphere in the flask was replaced with argon. Dry THF (3.0 ml) and distilled water (0.98 ml) were added to the flask via a syringe, and the mixture was degassed with argon and stirred at room temperature for 1 h. Into the flask was added a solution of 2,5-dibromothiophene (2) mg ( mmol), phenylboronic acid neopentylglycol ester (1) mg ( mmol), and naphthalene mg ( mmol) as an internal standard in dry THF (9.0 ml) via a cannula at room temperature. The reaction was allowed to proceed for 24 h followed by quenching with 6 M hydrochloric acid. The organic layer was analyzed by GC. Conversions of 1 = 63%, conversion of 2 = 51%; yield of 3 = 0%, yield of 4 = 33% (3/4 = 0/100). 9. Block copolymerization of 6a and then 6b All glass apparatus was dried prior to use. Addition of reagents to a reaction flask and withdrawal of a small aliquot of the reaction mixture for analysis were carried out via a syringe from a threeway stopcock under a stream of nitrogen. A round-bottomed flask equipped with a three-way stopcock was heated under reduced pressure, and then cooled to room temperature under an argon atmosphere. Initiator g ( mmol), CsF g (0.290 mmol), and 18-crown g (0.582 mmol) were placed in the flask, and the atmosphere in the flask was replaced with S7

8 argon. Dry THF (4.0 ml) and distilled water (0.22 ml) were added to the flask via a syringe, and the mixture was degassed with argon and stirred at room temperature for 1 h. A solution of monomer 6a g ( mmol) in dry THF (2.0 ml, degassed with argon) was added to the mixture of initiator, via a cannula, and the reaction mixture was stirred for 1 h at room temperature. Then, a solution of the second monomer 6b g (0.049 mmol) in dry THF (1.0 ml, degassed with argon) was added to the reaction mixture. After 24 h, 6 M hydrochloric acid was added, and the mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was dissolved in THF and the solution was added to methanol to precipitate the product ( g, 87%). Similarly block copolymerization of 6b and then 6a afforded the product ( g, 96%). 10. GPC profile of P3HT obtained by mixing tolyl(pt-bu 3 )PdBr and CsF prior to polymerization Figure S1. GPC profile of P3HT obtained by polymerization of 6a with tolyl(pt-bu3)pdbr, which was mixed with CsF prior to polymerization for 1 h, at rt (Mn = 10300, Mw/Mn =1.45). 11. NMR spectra S8

9 Figure S2. 1 H NMR spectrum of P3HT obtained by polymerization of 6a with an initiator generated in situ from AmPhos Pd G2 and 5 at rt (CDCl3, 25 o C). S9

10 Figure S3. 1 H NMR spectrum of polyfluorene obtained by polymerization of 6b with an initiator generated in situ from AmPhos Pd G2 and 5 at rt (CDCl3, 25 o C). S10

11 Figure S4. 1 H NMR spectrum of AmPhos Pd initiator 7 (CDCl3, 25 o C). S11

12 Figure S5. 13 C NMR spectrum of AmPhos Pd initiator 7 (CDCl3, 25 o C). S12

13 Figure S6. 31 P NMR spectrum of AmPhos Pd initiator 7 (CDCl3, 25 o C). S13

14 Figure S7. 1 H NMR spectrum of P3HT obtained by polymerization of 6a with AmPhos Pd initiator 7 at rt (Table 2, entry 4) (CDCl3, 25 o C). S14

15 Figure S8. 1 H NMR spectrum of polyfluorene obtained by polymerization of 6b with AmPhos Pd initiator 7 at rt (Table 2, entry 7) (CDCl3, 25 o C). S15

16 Figure S9. 1 H NMR spectrum of block copolymer obtained by polymerization of 6b and then 6a with AmPhos Pd initiator 7 at rt (Figure 3a) (CDCl3, 25 o C). S16

17 Figure S10. 1 H NMR spectrum of block copolymer obtained by polymerization of 6a and then 6b with AmPhos Pd initiator 7 at rt (Figure 3b) (CDCl3, 25 o C). 12. Supporting References 1. Yokozawa, T.; Suzuki, R.; Nojima, M.; Ohta, Y.; Yokoyama, A., Precision Synthesis of Poly(3-hexylthiophene) from Catalyst-Transfer Suzuki Miyaura Coupling Polymerization. Macromol. Rapid Commun. 2011, 32 (11), Dong, C.-G.; Hu, Q.-S., Preferential Oxidative Addition in Palladium(0)-Catalyzed Suzuki Cross-Coupling Reactions of Dihaloarenes with Arylboronic Acids. J. Am. Chem. Soc. 2005, 127 (28), Zhang, X.; Tian, H.; Liu, Q.; Wang, L.; Geng, Y.; Wang, F., Synthesis of Fluorene- Based Oligomeric Organoboron Reagents via Kumada, Heck, and Stille Cross-Coupling Reactions. J. Org. Chem. 2006, 71 (11), S17