Supporting Information

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1 Supporting Information Efficient Catalytic Epoxidation in Water by Axial N-Ligand-Free Mn-Porphyrins within a Micellar Capsule Takumi Omagari, Akira Suzuki, Munetaka Akita, Michito Yoshizawa* Chemical Resources Laboratory, Tokyo Institute of Technology, 29 Nagatsuta, Midori-ku, Yokohama , Japan; * yoshizawa.m.ac@m.titech.ac.jp Contents Materials and methods Synthesis of 2 3 M (M = Mn-, Zn, Ni, and Co) and 2 Mn- (UV-visible and 1 H NMR spectra, DLS analysis) General procedure for the catalytic epoxidation of styrenes by ( 1 H NMR spectra and GC chart) Control experiments of the catalytic epoxidation of Catalytic epoxidation of various styrenes UV-visible spectra of 3 Mn-O-Mn and 3 Mn- before/after the catalytic reaction within 2 UV-visible spectra of 3 Mn- and 3 Mn=O within/without 2 UV-visible spectra of and 3 Mn- after the addition of and 6 Time course of the epoxidation of by without imidazole S1

2 Materials and methods NMR: Bruker AVANCE- ( MHz), MALDI-TOF MS: Shimadzu AXIMA-CFR Plus, ESI-TOF MS: Bruker microtof II, Particle Size Analysis (DLS): Wyatt Technology DynaPro Nanostar, FT-IR: JASCO FT/IR-2, UV-vis: JASCO V-67DS, Gas Chromatograph: Shimadzu GC-21AFsc. Solvents and reagents: TCI Co., Ltd., Wako Pure Chemical Industries Ltd., Kanto Chemical Co., Inc., Sigma-Aldrich Co., and Cambridge Isotope Laboratories, Inc. Compounds: 1, 2, and metallo-porphyrins 3 M and Mn- were synthesized according to previously published procedures. [1,2] References [1] Kondo, K.; Suzuki, A.; Akita, M.; Yoshizawa, M. Angew. Chem. Int. Ed. 213, 2, [2] Alder, A. D.; Longo, F. R.; Kampas, F.; Kim, J. J. Inorg. Nucl. Chem. 197, 32, [3] Guo, C. C.; Li, H. P.; Xu, J. B. J. Catal. 1999, 18, S2

3 Synthesis of 2 3 M and 2 Mn- 1) grinding + Mn 2) H 2 O, r.t. 3) filtration Mn A mixture of amphiphilic compound 1 (1. mg, 2. µmol) and tetraphenylporphine manganese(iii) chloride (3 Mn- ;.7 mg, 1. µmol) was ground for min by using an agate mortar and pestle followed by the addition of H 2 O (1. ml) at r.t. After an excess 3 Mn- was removed by centrifugation and filtration, a clear green solution of 2 containing 3 Mn- (63%) was obtained. The formation of composite was confirmed by 1 H NMR, UV-visible, and DLS analyses. By using zinc(ii) tetraphenylporphine 3 Zn, nickel(ii) tetraphenylporphine 3 Ni, cobalt(ii) tetraphenylporphine 3 Co, and fluorinated tetraphenylporphyrin manganese(iii) chloride Mn-, host-guest composites 2 3 Zn, 2 3 Ni, 2 3 Co, and 2 Mn- were also prepared by the same procedure. The host-guest ratios were estimated by UV-visible analysis in CH 2 2 after freeze-drying of the aqueous solutions. a) Mn- 76 (SDS) n 3 Mn- b) nm nm S3

4 c) Zn 3 Zn d) nm Ni Ni e) nm Co 3 Co 3 6 nm Figure S1. UV-visible spectra (r.t.) of 3 M in CH 2 2 (. mm) and 2 3 M in H 2 O (1. mm based on 1). M = a) Mn-, c) Zn, d) Ni, and e) Co. b) UV-visible spectrum (r.t.) of in CH 2 2 after freeze-drying of the aqueous solution. 27 S

5 Mn- 2 Mn nm Figure S2. UV-visible spectra (r.t.) of Mn- in CH 2 2 (. mm) and 2 Mn- in H 2 O (1. mm based on 1). a) b) g c f d a e b h i j j i + h N O g f e a b c d c) ppm Figure S3a. 1 H NMR spectra ( MHz, D 2 O, r.t.) of a) 2, b), and c) 2 3 Zn. a) b) logd logd 9.8 d = 1. nm 9.8 d = 1. nm ppm ppm Figure S3b. DOSY NMR spectra ( MHz, D 2 O, r.t.) of a) 2 and b) 2 3 Zn. S

6 week 8 h h 3 6 nm Figure S. UV-visible spectra (H 2 O, r.t., 1. mm based on 1) of by the preparation through stirring a mixture of capsule 2 and 3 Mn- in H 2 O at r.t. without grinding. 8 d av = 1.1 nm 8 d av = 2. nm % mass 2 % mass nm nm Figure S. Size distribution of 2 and in H 2 O (1. mm based on 1) by DLS measurement at r.t. General procedure for the catalytic epoxidation of styrenes by O H 2 O, r.t. PhIO, imidazole 6 A H 2 O solution (1. ml) of (.2 µmol based on 3 Mn- ), imidazole (.7 mg, 1 µmol), and iodosylbenzene (. mg, 2 µmol) were added to a microtube containing -chlorostyrene (13.9 mg, 1 µmol). The reaction mixture was vigorously stirred (6 rpm) for h at r.t. under air. Na (~1 mg) was added to the resultant solution and then the products were extracted with CD 3 (2.2 ml). The organic layer was separated after centrifuging for 1 min at 13 rpm. The obtained products S6

7 were analyzed by 1 H NMR after adding tetraethylsilane (7.2 mg, µmol) as an internal standard to the organic solution. After the addition of naphthalene (12.8 mg, 1 µmol) as an internal standard, the products were further analyzed by GC. I O Figure S6. 1 H NMR spectrum ( MHz, CD 3, r.t.) of crude products after the catalytic epoxidation of by (Table 1, entry 1). S7

8 Peak No Time [min] Area Intensity Compounds Totals Figure S7a. GC chart of crude products after the catalytic epoxidation of by. Peak No Time [min] Area Intensity Compounds Totals Figure S7b. GC chart of crude products after the catalytic epoxidation of by 2 Mn-. S8

9 Table S1. Control experiments of the catalytic epoxidation of. conditions O H 2 O, r.t., h 6 entry catalyst [µmol] imidazole [µmol] PhIO [µmol] yield [%] TON 1 (.2) (.2) (.2) Conditions: catalyst (.2 or μmol), (1 μmol), imidazole (1 or μmol), PhIO (2 or μmol) in H 2 O at r.t. for h. Table S2. The catalytic epoxidation of various styrenes. catalyst O X H 2 O, r.t., 1 or h PhIO, imidazole X entry catalyst [µmol] substrate time [h] imidazole [µmol] yield [%] TON 1 2' 3 Mn- (.2) Mn- (.1) 1 3 (SDS) n 3 Mn- (.1) (.2) Mn- (.6) Mn- (.6) Mn- (.6) HO 9 2 C 1 R N N + 2 O O 2 X 2' R n 2 R = H X = NO 3 R = H X = R = X = Conditions: catalyst (.1-.2 μmol), styrenes (1 μmol), imidazole (1 or μmol), PhIO (2 μmol) in H 2 O at r.t. for 1 or h. S9

10 71 77 Normalized 3 Mn-O-Mn 3 Mn- 3 Mn- (after the reaction) nm [3] Figure S8. UV-visible spectra (CH 2 2, r.t.) of 3 Mn-O-Mn and 3 Mn- before/after the catalytic reaction within capsule Mn=O 77 3 Mn Mn=O nm Figure S9. UV-visible spectra (r.t.) of 3 Mn- and 3 Mn=O in CH 2 2 (. mm) and and 2 3 Mn=O (1. mm based on 1) in H 2 O Mn- 3 Mn- + 3 Mn nm Figure S1. UV-visible spectra of 3 Mn- before and after the addition of or 6 ( equiv. each) in CH 2 2 (dot lines) and before and after the addition of or 6 ( equiv. each) in H 2 O (solid lines). S1

11 .8 H 2 O Mn 6 H 2 O Mn nm.8 6 H 2 O H 2 O Mn nm Figure S11. UV-visible spectra of after the addition of and/or 6 (2 equiv. each) in H 2 O. TON yield [%] yield TON time [h] Figure S12. Time course of the epoxidation of by without imidazole in H 2 O. S11