Supporting Information

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1 Supporting Information Dehydrogenative xidation of Alcohols in Aqueous Media Using Water-Soluble and Reusable Cp*Ir Catalysts Bearing a Functional Bipyridine Ligand Ryoko Kawahara, a Ken-ichi Fujita,*,a,b and Ryohei Yamaguchi*,a a Graduate School of Human and Environmental Studies, Kyoto University, Sakyo-ku Kyoto , Japan b Graduate School of Global Environmental Studies, Kyoto University, Sakyo-ku Kyoto , Japan Experimental General: 1 H and 13 C{ 1 H} NMR spectra were recorded on JEL ECX-500 and ECS-400 spectrometers. Gas chromatography (GC) analyses were performed on a GL-Sciences GC353B gas chromatograph with a capillary column (GL-Sciences InertCap 5 and InertCap Pure WAX). Elemental analyses were carried out at the Microanalysis Center of Kyoto University. Melting points were measured using a Yanagimoto micro melting point apparatus. Silica-gel column chromatography was carried out by using 1) Wako-gel C-200. The complexes, [Cp*IrCl 2 ] 2 (Cp* = η 5 -pentamethylcyclopentadienyl), 2) 3) [Cp*Ir(H 2 ) 3 ]X 2 (X = Tf, PF 6, BF 4 ), 6-hydroxy-2,2 -bipyridine (1a), 4) 5) 6,6 -dihydroxy-2,2 -bipyridine (1b), [Cp*Ir(2,2 -bipyridine)(h 2 )](Tf) 2 (5), and [Cp*Ir(4,4 -dihydroxy-2,2 -bipyridine)(h 2 )](Tf) 2 (6) 6) were prepared according to the literature method. All other reagents are commercially available and were used as received. S1

2 Preparation of [Cp*Ir(6-hydroxy-2,2 -bipyridine)(h 2 )](Tf) 2 (2a) shown in Eq. 1: Under an atmosphere of argon, [Cp*Ir(H 2 ) 3 ](Tf) 2 (135.9 mg, 0.20 mmol) was placed in a flask. Water (4 ml) and 6-hydroxy-2,2 -bipyridine (1a) (34.7 mg, 0.20 mmol) were added, and the mixture was stirred for 24 h at room temperature. Evaporation of the solvent in vacuo gave a yellow powder of 2a in 98% yield (160.1 mg, mmol). Yellow crystals of 2a were obtained by recrystallization from methanol-diethyl ether (140.5 mg, 0.17 mmol, 86 %). Mp C (dec.). 1 H NMR (500 MHz, D 2 ) δ 9.09 (d, J = 5 Hz, 1H, aromatic), 8.42 (d, J = 8 Hz, 1H, aromatic), 8.26 (t, J = 8 Hz, 1H, aromatic), 8.07 (t, J = 8 Hz, 1H, aromatic), 7.94 (d, J = 6 Hz, 1H, aromatic), 7.83 (t, J = 6 Hz, 1H, aromatic), 7.26 (d, J = 8 Hz, 1H, aromatic), 1.61 (s, 15H, Cp*). 13 C{ 1 H} NMR (125.8 MHz, D 2 ) δ (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (q, J CF = 317 Hz, CF 3 ), (s, aromatic), (s, aromatic), 89.9 (s, C 5 Me 5 ), 9.0 (s, C 5 Me 5 ). Anal. Calcd for C 22 H 25 8 F 6 N 2 S 2 Ir: C, 32.39; H, 3.09; N, Found: C, 32.60; H, 2.98; N, Preparation of [Cp*Ir(6,6 -dihydroxy-2,2 -bipyridine)(h 2 )](Tf) 2 (2b) shown in Eq. 1: Under an atmosphere of argon, [Cp*Ir(H 2 ) 3 ](Tf) 2 (407.8 mg, 0.60 mmol) was placed in a flask. Water (12 ml) and 6,6 -dihydroxy-2,2 -bipyridine (1b) (113.8 mg, 0.60 mmol) were added, and the mixture was stirred for 30 min at room temperature. Evaporation of the solvent in vacuo gave a yellow powder of 2b in 93% yield (464.1 mg, 0.56 mmol). Yellow crystals of 2b were obtained by recrystallization from methanol-diethyl ether (384.3 mg, 0.46 mmol, 77 %). Mp C (dec.). 1 H NMR (500 MHz, D 2 ) δ 8.02 (t, J = 8 Hz, 2H, aromatic), 7.83 (d, J = 8 Hz, 2H, aromatic), 7.19 (d, J = 8 Hz, 2H, aromatic), 1.56 (s, 15H, Cp*). 13 C{ 1 H} NMR (125.8 MHz, D 2 ) δ (s, aromatic), (s, aromatic), (s, aromatic), (q, J CF = 317 Hz, CF 3 ), (s, aromatic), (s, aromatic), 89.4 (s, C 5 Me 5 ), 9.2 (s, C 5 Me 5 ). Anal. Calcd for C 22 H 25 9 F 6 N 2 S 2 Ir: C, 31.77; H, 3.03; N, Found: C, 31.61; H, 2.93; N, Preparation of [Cp*Ir(6,6 -dihydroxy-2,2 -bipyridine)(h 2 )]X 2 (3: X = PF 6, 4: X = BF 4 ) shown in Eq. 1: According to the procedure described for 2b, complexes 3 and 4 were prepared from [Cp*Ir(H 2 ) 3 ]X 2 (0.15 mmol) and 6,6 -dihydroxy-2,2 -bipyridine (1b) (0.15 mmol) in water (3 ml). Complex 3: 91% yield (112.6 mg, mmol). Mp C (dec.). 1 H NMR (500 MHz, D 2 ) δ 8.01 (t, J = 8 Hz, 2H, aromatic), 7.82 (d, J = 8 Hz, 2H, aromatic), 7.17 (d, J = 8 Hz, 2H, aromatic), 1.55 (s, 15H, Cp*). 13 C{ 1 H} NMR (125.8 MHz, D 2 ) δ (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), 89.3 (s, C 5 Me 5 ), 9.2 (s, C 5 Me 5 ). Anal. Calcd for C 20 H 25 3 F 12 N 2 P 2 Ir: C, 29.17; H, 3.06; N, Found: C, 29.46; H, 3.23; N, Complex 4: 90% yield (95.6 mg, mmol). Mp C (dec.). 1 H NMR (500 MHz, D 2 ) δ 8.00 (t, J = 8 Hz, 2H, aromatic), 7.80 (d, J = 8 Hz, 2H, aromatic), 7.16 (d, J = 8 Hz, 2H, aromatic), 1.55 (s, 15H, Cp*). 13 C{ 1 H} NMR (125.8 MHz, D 2 ) δ (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), 89.3 (s, C 5 Me 5 ), 9.2 (s, C 5 Me 5 ). Anal. Calcd for C 20 H 25 3 B 2 F 8 N 2 Ir: C, 33.96; H, 3.56; N, Found: C, 33.58; H, 3.82; N, General Procedure for the Dehydrogenative xidation of Benzyl Alcohol (7a) to Benzaldehyde (8a) Catalyzed by Cp*Ir Complexes under Various Conditions Shown in Table 1: S2

3 Under an atmosphere of argon, catalyst ( mol% Ir), water (5 ml), and benzyl alcohol (7a) (0.25 mmol) were placed in a round bottom flask. The mixture was stirred under reflux for 6 or 20 h. Then the mixture was diluted with 2-propanol (25 ml). The conversion of benzyl alcohol (7a) and the yield of benzaldehyde (8a) was determined by GC analysis using biphenyl as an internal standard. General Procedure for the Dehydrogenative xidation of Primary Alcohols to Aldehydes in Water Shown in Table 2: Under an atmosphere of argon, catalyst 2b ( mol%), water (5 ml), and a primary alcohol (0.25 mmol) were placed in a round bottom flask. The mixture was stirred under reflux for 20 h. Then the mixture was diluted with 2-propanol (25 ml). The conversions of alcohols and the yields of aldehydes were determined by GC analysis using biphenyl as an internal standard. General Procedure for the Dehydrogenative xidation of Secondary Alcohols to Ketones in Water Shown in Table 3, Entries 1, 8-11: Under an atmosphere of argon, catalyst 2b ( mol%), water (4.5 or 5.0 ml), tert-butyl alcohol (0 or 0.5 ml), and a secondary alcohol (0.25 mmol) were placed in a round bottom flask. The mixture was stirred under reflux for 20 h. Then the product was extracted with dichloromethane (30 ml). The conversions of alcohols and the yields of ketones were determined by GC analysis using biphenyl as an internal standard. General Procedure for the Dehydrogenative xidation of Secondary Alcohols to Ketones in Water Shown in Table 3, Entries 2-7: Under an atmosphere of argon, catalyst 2b ( mol%), water (5 or 50 ml), and a secondary alcohol (0.25 or 2.5 mmol) were placed in a round bottom flask. The mixture was stirred under reflux for 20 or 100 h. Then the product was extracted with dichloromethane (30 ml). The conversions of alcohols and the yield of ketones were determined by the 1 H NMR analysis in chloroform-d using 1,3,5-trimethoxybenzene as an internal standard. Procedure for the Reuse of the Catalyst 2b in the Dehydrogenative xidation of Secondary Alcohol 9b in Water Shown in Eq. 2: In a round bottom flask, catalyst 2b (1.0 mol%), water (5 ml), and secondary alcohol 9b (0.25 mmol) were placed under air. The mixture was stirred under reflux for 20 h. The product was extracted with hexane (30 ml). By this procedure, the product 10b was extracted into organic phase, and the catalyst 2b was recovered into aqueous phase. The yield of 10b was determined by the 1 H NMR analysis in chloroform-d using 1,3,5-trimethoxybenzene as an internal standard. Aqueous phase including the catalyst 2b was used as a catalyst and solvent for the next run. Procedure for the Reuse of the Catalyst 2b in the Dehydrogenative xidation of Primary Alcohol 7e in Water Shown in Eq. S1: In a round bottom flask, catalyst 2b (3.0 mol%), water (5 ml), and primary alcohol 7e (0.25 mmol) were placed under air. The mixture was stirred under reflux for 20 h. The product was extracted with hexane (30 ml). By this procedure, the product 8e was extracted into organic phase, and the catalyst 2b was recovered into aqueous phase. The yield of 8e was determined by GC analysis using biphenyl as an S3

4 internal standard. Aqueous phase including the catalyst 2b was used as a catalyst and solvent for the next run. 7e cat. 2b (3.0 mol%) H 2 reflux, 20 h 8e CH + H 2 reuse yield of 8e (%) (S1) Procedure for the Reuse of the Catalyst 2b in the Dehydrogenative xidation of Various Primary and Secondary Alcohols in Aqueous Media Shown in Scheme 1: In a round bottom flask, catalyst 2b (2.1 mg, 2.5 µmol, 1.0 mol%), water (5 ml), and 9d (39.2 mg, 0.25 mmol) were placed under air. The mixture was stirred under reflux for 20 h. The product was extracted with hexane (30 ml). By this procedure, the product 10d was extracted into organic phase, and the catalyst 2b was recovered into aqueous phase. The yield of 10d was detemined by the 1 H NMR analysis in chloroform-d using 1,3,5-trimethoxybenzene as an internal standard. To the recovered aqueous phase including the catalyst 2b was added 7e (30.3 mg, 0.25 mmol) and the mixture was stirred under reflux for 20 h. The product was extracted with hexane (30 ml). By this procedure, the product 8e was extracted into organic phase, and the catalyst 2b was recovered into aqueous phase. The yield of 8e was determined by GC analysis using biphenyl as an internal standard. To the recovered aqueous phase including the catalyst 2b was added 9b (38.0 mg, 0.25 mmol) and the mixture was stirred under reflux for 20 h. The product was extracted with hexane (30 ml). By this procedure, the product 10b was extracted into organic phase, and the catalyst 2b was recovered into aqueous phase. The yield of 10b was determined by the 1 H NMR analysis in chloroform-d using 1,3,5-trimethoxybenzene as an internal standard. S4

5 Dual Reactions Involving Dehydrogenation of Alcohols and Hydrogenation of 1-Decene Mentioned in Reference 13: In order to obtain reliable experimental evidence that the evolved gas in the oxidation of alcohols is hydrogen (H 2 ), we carried out the following dual reactions (Scheme S1). The reaction of 9b using the catalyst 2b was conducted in a flask that was connected through a rubber tube to another flask in which 1-decene and a catalytic amount of RhCl(PPh 3 ) 3 in benzene were placed. When the dehydrogenation of 9b was almost completed, decane was produced in 94% yield in the latter flask, demonstrating that the hydrogen gas generated in the former flask was transferred through the tube to reduce 1-decene in the latter flask. In case of the dehydrogenation of 7e, similar dual reactions also gave decane in 90% yield. Thus, it is apparent that hydrogen gas generated in the present dehydrogenation is pure enough to be utilized in other reactions. cat. 2b (1.0 mol%) Me 9b 1.0 mmol H 2 reflux, 20 h H 2 Me 98% 10b 1-decene 1.0 mmol cat. RhCl(PPh 3 ) 3 (2.0 mol%) benzene 50 o C, 20 h decane 94% 7e 1.0 mmol cat. 2b (1.5 mol%) H 2 reflux, 20 h H 2 H 8e 94% 1-decene 1.0 mmol cat. RhCl(PPh 3 ) 3 (2.0 mol%) benzene 50 o C, 20 h decane 90% Scheme S1. General Procedure for the Dual Reactions Involving Dehydrogenation of Alcohols and Hydrogenation of 1-Decene Shown in Scheme S1: In a flask, under an atmosphere of argon, catalyst 2b (1.0 or 1.5 mol%), water (20 ml) and alcohol (1.0 mmol) were placed. In another flask, under an atmosphere of argon, RhCl(PPh 3 ) 3 (2.0 mol%), benzene (1.5 ml) and 1-decene (1.0 mmol) were placed. The two flasks were connected through a rubber tube. S5

6 The mixture in the former flask was stirred under reflux for 20 h, while the mixture in the latter was stirred at 50 o C. The yield of decane was determined by GC analysis using undecane as an internal standard. The yield of p-methoxyacetophenone was determined by the 1 H NMR analysis in chloroform-d using 1,3,5-trimethoxybenzene as an internal standard. The yield of p-tolualdehyde was determined by GC analysis using biphenyl as an internal standard. Isolation of the Products in Dehydrogenative xidation of Alcohols Mentioned in Reference 14: Dehydrogenative oxidation reactions of various primary and secondary alcohols in water proceeded to give the corresponding aldehydes and ketones in high yields with almost complete selectivity. The produced carbonyl compounds were isolated by column chromatography on silica-gel. Results are shown in Table S1. Table S1. Isolation of the Products in Dehydrogenative xidation of Various Primary and Secondary Alcohols in Water a catalyst 2b R 1 R 2 H 2 R 1 R 2 7 or 9 reflux, 20 h 8 or 10 + H 2 entry alcohol cat. 2b [mol%] product isolated yield [%] b R R = 4-Me R = 4-Me R = 4-Cl R = 4-Br R = 4-Ph (7b) (7e) (7f) (7g) (7j) b 8e 8f 8g 8j R' R' = 4-Me R' = 4-Cl R' = 4-Br (9b) (9d) (9e) b 10d 10e b (9h) h (9k) k (9l) l 80 a The reaction was carried out with alcohol (0.50 mmol) and the catalyst 2b ( mol%) in water (10 ml) under reflux for 20 h. b Water (9 ml) and tert-butyl alcohol (1 ml) were added. General Procedure for the Dehydrogenative xidation of Various Primary and Secondary Alcohols in Water Shown in Table S1: Under an atmosphere of argon, catalyst 2b ( mol%), water (9 or 10 ml), tert-butyl alcohol (0 or 1 ml), and an alcohol (0.50 mmol) were placed in a round bottom flask. The mixture was stirred under S6

7 reflux for 20 h. The product was extracted with dichloromethane (30 ml). After evaporation of the solvent, the product was purified by column chromatography on silica-gel (eluent: ethyl acetate/hexane). Spectral Data for the Isolated Products in Table S1: p-methoxybenzaldehyde (8b) 7) (Table S1, entry 1): 1 H NMR (400 MHz, CDCl 3 ) δ 9.85 (s, 1H, CH), 7.81 (d, J = 9 Hz, 2H, aromatic), 6.97 (d, J = 9 Hz, 2H, aromatic), 3.84 (s, 3H, CH 3 ). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, CH), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), 55.3 (s, CH 3 ). p-tolualdehyde (8e) 8) (Table S1, entry 2): 1 H NMR (500 MHz, CDCl 3 ) δ 9.91 (s, 1H, CH), 7.73 (d, J = 8 Hz, 2H, aromatic), 7.27 (d, J = 8 Hz, 2H, aromatic), 2.37 (s, 3H, CH 3 ). 13 C{ 1 H} NMR (125.8 MHz, CDCl 3 ) δ (s, CH), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), 21.4 (s, CH 3 ). p-chlorobenzaldehyde (8f) 9) (Table S1, entry 3): 1 H NMR (400 MHz, CDCl 3 ) δ 9.99 (s, 1H, CH), 7.83 (d, J = 8 Hz, 2H, aromatic), 7.51 (d, J = 8 Hz, 2H, aromatic). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, CH), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic). p-bromobenzaldehyde (8g) 10) (Table S1, entry 4): 1 H NMR (400 MHz, CDCl 3 ) δ 9.97 (s, 1H, CH), 7.74 (d, J = 8 Hz, 2H, aromatic), 7.66 (d, J = 8 Hz, 2H, aromatic). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, CH), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic). p-phenylbenzaldehyde (8j) 11) (Table S1, entry 5): 1 H NMR (400 MHz, CDCl 3 ) δ 9.99 (s, 1H, CH), 7.89 (d, J = 8 Hz, 2H, aromatic), 7.68 (d, J = 8 Hz, 2H, aromatic), 7.57 (d, J = 8 Hz, 2H, aromatic), (m, 3H, aromatic). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, CH), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic). 4 -Methoxyacetophenone (10b) 12) (Table S1, entry 6): 1 H NMR (400 MHz, CDCl 3 ) δ 7.92 (d, J = 9 Hz, 2H, aromatic), 6.91 (d, J = 9 Hz, 2H, aromatic), 3.84 (s, 3H, CH 3 ), 2.53 (s, 3H, CH 3 ). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, C), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), 55.3 (s, CH 3 ), 26.2 (s, CH 3 ). 4 -Chloroacetophenone (10d) 13) (Table S1, entry 7): 1 H NMR (400 MHz, CDCl 3 ) δ 7.87 (d, J = 8 Hz, 2H, aromatic), 7.41 (d, J = 8 Hz, 2H, aromatic), 2.57 (s, 3H, CH 3 ). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, C), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), 26.0 (s, CH 3 ). 4 -Bromoacetophenone (10e) 14) (Table S1, entry 8): 1 H NMR (400 MHz, CDCl 3 ) δ 7.79 (d, J = 8 Hz, 2H, aromatic), 7.57 (d, J = 8 Hz, 2H, aromatic), 2.57 (s, 3H, CH 3 ). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, C), (s, aromatic), (s, aromatic), (s, aromatic), (s, aromatic), 26.4 (s, CH 3 ). 2-ctanone (10h) 15) (Table S1, entry 9): 1 H NMR (400 MHz, CDCl 3 ) δ 2.43 (t, J = 7 Hz, 2H, CH 2 ), 2.12 (s, 3H, CH 3 ), 1.56 (m, 2H, CH 2 ), 1.28 S7

8 (br, 6H, CH 2 ), 0.88 (t, J = 7 Hz, 3H, CH 3 ). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, C), 43.2 (s, CH 2 ), 31.3 (s, CH 2 ), 29.2 (s, CH 2 ), 28.5 (s, CH 3 ), 23.4 (s, CH 2 ), 22.1 (s, CH 2 ), 13.6 (s, CH 3 ). Cycloheptanone (10k) 16) (Table S1, entry 10): 1 H NMR (400 MHz, CDCl 3 ) δ 2.47 (m, 4H, CH 2 ), 1.69 (br, 8H, CH 2 ). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, C), 43.1 (s, CH 2 ), 29.8 (s, CH 2 ), 23.7 (s, CH 2 ). Cyclooctanone (10l) 17) (Table S1, entry 11): 1 H NMR (400 MHz, CDCl 3 ) δ 2.41 (m, 4H, CH 2 ), 1.88 (m, 4H, CH 2 ), 1.55 (m, 4H, CH 2 ), 1.38 (m, 2H, CH 2 ). 13 C{ 1 H} NMR (100.5 MHz, CDCl 3 ) δ (s, C), 42.0 (s, CH 2 ), 27.2 (s, CH 2 ), 25.7 (s, CH 2 ), 24.7 (s, CH 2 ). S8

9 Reuse of the Catalyst 2b in the Dehydrogenative xidation of Various Primary and Secondary Alcohols in Aqueous Media Mentioned in Reference 17: In addition to the reuse of the catalyst 2b shown in eq. 2, eq. S1, and Scheme 1, we also examined the reuse of 2b in the dehydrogenative oxidation of various primary and secondary alcohols. The results are shown in Table S2. Table S2. Reuse of the Catalyst 2b in the Dehydrogenative xidation of Various Primary and Secondary Alcohols in Aqueous Media a catalyst 2b R 1 R 2 H 2 R 1 R 2 reflux, 20 h 7 or 9 8 or 10 + H 2 entry alcohol cat. 2b [mol%] run yield [%] b conv. [%] b 98 1 Me (9b) 1.0 1st 2nd 3rd 4th 5th 6th 7th 8th Br Cl F 3 C (9a) (9d) (9k) (7e) (7a) (7g) (7h) st 2nd 3rd 1st 2nd 3rd 1st 2nd 3rd 1st 2nd 3rd 4th 5th 6th 7th 8th 1st 2nd 3rd 1st 2nd 3rd 1st 2nd 3rd a The reaction was carried out with alcohol (0.25 mmol) and the catalyst 2b ( mol%) in water (5 ml) under reflux for 20 h. After the reaction was completed, the product was extracted with hexane or dichloromethane (30 ml). The aqueous phase including the catalyst 2b was subjected to the next run. b Determined by 1 H NMR (entries 1-3). Determined by GC (entries 4-8) S9

10 General Procedure for the Reuse of the Catalyst 2b in the Dehydrogenative xidation of Various Secondary Alcohols in Water Shown in Table S2, Entries 1-3: In a round bottom flask, catalyst 2b (1.0 mol%), water (5 ml), and a secondary alcohol (0.25 mmol) were placed under air. The mixture was stirred under reflux for 20 h. The product was extracted with hexane (30 ml). By this procedure, the product was extracted into organic phase, and the catalyst 2b was recovered into aqueous phase. The conversions of alcohols and the yields of ketones were determined by the 1 H NMR analysis in chloroform-d using 1,3,5-trimethoxybenzene as an internal standard. Aqueous phase including the catalyst 2b was used as a catalyst and solvent for the next run. General Procedure for the Shown in Table S2, Entries 4-8: In a round bottom flask, catalyst 2b ( mol%), water (5 ml), and an alcohol (0.25 mmol) were placed under air. The mixture was stirred under reflux for 20 h. The product was extracted with hexane (30 ml) [dichloromethane (30 ml) was used in the case of the reaction of p-bromobenzyl alcohol (entry 7)]. By this procedure, the product was extracted into organic phase, and the catalyst 2b was recovered into aqueous phase. The conversions of alcohols and the yields of the products were determined by GC analysis using biphenyl as an internal standard. Aqueous phase including the catalyst 2b was used as a catalyst and solvent for the next run. Preparation and Catalytic Activity of the Complex 11 Mentioned in Reference 18: Treatment of 2b with Na t Bu (1.0 equiv.) in water gave a monocationic complex 11 in 82% yield (eq. S2). The complex 11 exhibited a high catalytic activity in the oxidation of 7a to give 8a in 93% yield (eq. S3), indicating its importance as a catalytically active species. 2+ 2Tf - + Tf - H N Ir 2 N Na t Bu 1 equiv. H 2, r.t. H N Ir 2 N (S2) 2b 11 (82%) catalyst 11 (1.5 mol%) H 2 reflux, 20 h H + 7a 8a (93%) H 2 (S3) Procedure for the Preparation of the Complex 11 Shown in Eq. S2: In a flask, the complex 2b (415.9 mg, 0.50 mmol) was placed. Water (15 ml) and Na t Bu (48.0 mg, 0.50 mmol) were added, and the mixture was stirred for 30 min at room temperature. Yellow solution gradually changed to yellow-green suspension. The suspension was filtered. The residue was washed with water and dried to give the complex 11 as a yellow-green powder (279.5 mg, 0.41 mmol, 82 %). Mp C (dec.). 1 H NMR (400 MHz, CD 3 D) δ 7.61 (t, J = 8 Hz, 2H, aromatic), 7.22 (d, J = 8 Hz, S10

11 2H, aromatic), 6.64 (d, J = 8 Hz, 2H, aromatic), 1.59 (s, 15H, Cp*). 13 C{ 1 H} NMR (125.8 MHz, CD 3 D) δ (s, aromatic), (s, aromatic), (s, aromatic), (q, J CF =319 Hz, CF 3 ), (s, aromatic), (s, aromatic), 89.0 (s, C 5 Me 5 ), 9.8 (s, C 5 Me 5 ). Anal. Calcd for C 21 H 24 6 F 3 N 2 S 1 Ir: C, 37.0; H, 3.55; N, Found: C, 37.33; H, 3.52; N, Procedure for the Dehydrogenative xidation of Benzyl Alcohol (7a) to Benzaldehyde (8a) Catalyzed by Complex 11 in Water Shown in Eq. S3: Under an atmosphere of argon, catalyst 11 (2.6 mg, 3.8 µmol, 1.5 mol%), water (5 ml), and benzyl alcohol (7a) (26.8 mg, 0.25 mmol) were placed in a round bottom flask. The mixture was stirred under reflux for 20 h. Then the product was extracted with dichloromethane (30 ml). The yield of benzaldehyde (8a) was determined by GC analysis using biphenyl as an internal standard. X-ray Structure Analysis of 2b: The single crystals of 2b contained two molecules of water as a solvent molecule. Diffraction data for 2b (H 2 ) 2 were obtained with a Rigaku RAXIS RAPID instrument. Reflection data were corrected for Lorentz and polarization effects. Empirical absorption corrections were applied. The structure was solved by Patterson methods (DIRDIF99 PATTY) 18),19) and refined anisotropically for non-hydrogen atoms by full-matrix least-squares calculations. Atomic scattering factors and anomalous dispersion terms were taken from the literature. 20) Hydrogen atoms were located on the idealized positions, however, hydrogen atoms of the coordinated water molecule were not located. The calculations were performed using the program system CrystalStructure. 21),22) RTEP drawing of the cationic part of 2b is shown in Figure S1. The crystal data and details are shown in CIF file. Figure S1. RTEP drawing of the cationic part of 2b with 50% thermal probability ellipsoids. Hydrogen atoms are omitted for clarity. S11

12 References 1) R. G. Ball, W. A. G. Graham, D. M. Heinekey, J. K. Hoyano, A. D. McMaster, B. M. Mattson, S. T. Michel, Inorg. Chem., 1990, 29, ) S. go, N. Makihara, Y. Watanabe, rganometallics 1999, 18, ) United State Patent (No ). 4) T. Umemoto, M. Nagayoshi, K. Adachi, G. Tomizawa, J. rg. Chem. 1998, 63, ) S. go, N. Makihara, Y. Kaneko, Y. Watanabe, rganometallics 2001, 20, ) (a) Y. Himeda, Green Chem. 2009, 11, (b) Y. Himeda, N. nozawa-komatsuzaki, S. Miyazawa, H. Sugihara, T. Hirose, K. Kasuga, Chem. Eur. J. 2008, 14, ) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 2; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 941A. 8) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 2; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 108A. 9) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 2; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 940B 10) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 2; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 109B. 11) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 2; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 972A. 12) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 2; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 34D. 13) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 2; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 27B. 14) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 2; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 832C. 15) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 1; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 638C. 16) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 1; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 674C. 17) The Aldrich Library of 13 C and 1 H FT NMR Spectra, 1st ed., Vol. 1; C. J. Pouchert, J. Behnke, Eds.; Aldrich Chemical Company Inc.: Milwaukee, 1993, 675C. 18) PATTY: P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, S. Garcia-Granda, R.. Gould, J. M. M. Smits, C. Smykalla, Technical Report of the Crystallography Laboratory; University of Nijmegen, ) P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, R. de Gelder, R. Israel, J. M. M. Smits, The DIRDIF-99 program system, Technical Report of the Crystallography Laboratory University of Nijmegen, Nijmegen, The Netherlands, S12

13 20) (a) D. T. Cromer, G. T. Waber, International Table for X-Ray Crystallography, The Kynoch Press, Birmingham, U.K., 1974; vol. IV, table 2.2 A; (b) J. A. Ibers, W. C. Hamilton, Acta Crystallogr. 1964, 17, 871; (c) D. C. Creagh, W. J. McAuley, in International Tables for X-Ray Crystallography, ed. A. J. C. Wilson, Kluwer Academic Publishers, Boston, 1992; vol. C, pp , table ; (d) D. C. Creagh, J. H. Hubbell, in International Tables for X-Ray Crystallography, ed. A. J. C. Wilson, Kluwer Academic Publishers, Boston, 1992; vol. C, pp , table ) CrystalStructure3.8, Crystal Structure Analysis Package, Rigaku and Rigaku/Molecular Structure Corp., ) J. R. Carruthers, J. S. Rollett, P.W. Betteridge, D. Kinna, L. Pearce, A. Larsen, E. Gabe, CRYSTALS Issue 11, Chemical Crystallography Laboratory, xford, S13

14 Me H p-methoxybenzaldehyde (Table S1, entry 1, 8b) 1 H NMR Me H p-methoxybenzaldehyde (Table S1, entry 1, 8b) 13 C NMR S14

15 H p-tolualdehyde (Table S1, entry 2, 8e) 1 H NMR H p-tolualdehyde (Table S1, entry 2, 8e) 13 C NMR S15

16 Cl H p-chlorobenzaldehyde (Table S1, entry 3, 8f) 1 H NMR Cl H p-chlorobenzaldehyde (Table S1, entry 3, 8f) 13 C NMR S16

17 Br H p-bromobenzaldehyde (Table S1, entry 4, 8g) 1 H NMR Br H p-bromobenzaldehyde (Table S1, entry 4, 8g) 13 C NMR S17

18 H p-phenylbenzaldehyde (Table S1, entry 5, 8j) 1 H NMR H p-phenylbenzaldehyde (Table S1, entry 5, 8j) 13 C NMR S18

19 Me 4'-Methoxyacetophenone (Table S1, entry 6, 10b) 1 H NMR Me 4'-Methoxyacetophenone (Table S1, entry 6, 10b) 13 C NMR S19

20 Cl 4'-Chloroacetophenone (Table S1, entry 7, 10d) 1 H NMR Cl 4'-Chloroacetophenone (Table S1, entry 7, 10d) 13 C NMR S20

21 Br 4'-Bromoacetophenone (Table S1, entry 8, 10e) 1 H NMR Br 4'-Bromoacetophenone (Table S1, entry 8, 10e) 13 C NMR S21

22 2-ctanone (Table S1, entry 9, 10h) 1 H NMR 2-ctanone (Table S1, entry 9, 10h) 13 C NMR S22

23 Cycloheptanone (Table S1, entry 10, 10k) 1 H NMR Cycloheptanone (Table S1, entry 10, 10k) 13 C NMR S23

24 Cyclooctanone (Table S1, entry 11, 10l) 1 H NMR Cyclooctanone (Table S1, entry 11, 10l) 13 C NMR S24