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1 A sustainable catalytic pyrrole synthesis Stefan Michlik, 1 Rhett Kempe* 1 1 Lehrstuhl Anorganische Chemie II, Universität Bayreuth, Bayreuth, Germany *To whom correspondence should be addressed. kempe@uni-bayreuth.de Contents General Considerations... 2 Screening Reactions... 2 Ligand and Complex Syntheses... 7 Reaction of 1-Phenylethanol with various Amino Alcohols Reaction of 2-Amino-3-phenyl-propan-1-ol with various Secondary Alcohols Reaction of 2-Amino-3-phenyl-propan-1-ol with various Cyclic Alcohols Reaction of Hexane-2,5-diol with various Amino Alcohols to Symmetric and Unsymmetric Bipyrroles Syntheses of -protected Amino Alcohols and their Conversion with 2-Amino-3-phenyl-propan-1-ol Mechanistic Studies Crystal Structure of [(4-Ph)Tr(P( i Pr) 2 )(HP( i Pr) 2 )Ir(cod)] (Catalyst II) Crystal Structure of [(4-Ph)Tr(HP(iPr) 2 )IrH 3 ] (catalyst resting state) MR-Data ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

2 General Considerations All reactions were carried out in a dry argon or nitrogen atmosphere using standard Schlenk techniques or glove box techniques. Halogenated solvents were dried over P 2 O 5, and nonhalogenated solvents were dried over sodium benzophenone ketyl. Deuterated solvents were ordered from Cambridge Isotope Laboratories, vented, stored over molecular sieves and distilled. All chemicals were purchased from commercial sources with purity with over 97% and used without further purification. MR spectra were received using an IOVA 400 and 300 MHz spectrometer at 298 K or a BRUKER 300 MHz spectrometer at 300 K. Chemical shifts are reported in ppm relative to the deuterated solvent. Elemental analyses were carried out on a Vario elementar EL III. GC analyses were carried out on an Agilent 6890 etwork GC system equipped with a HP-5 column (30 m x 0.32 µm x 0.25 µm). GC/MS analyses were carried out on a Thermo Focus GC/Trace DSQ system equipped with a HP-5MS column (30 m x 0.32 µm x 0.25 µm). X-ray crystal structure analyses were performed with a STOE-IPDS II equipped with an Oxford Cryostream low-temperature unit. Screening Reactions General screening procedure: In a pressure tube catalyst, solvent, secondary alcohol, amino alcohol and base were combined. The pressure tube was closed with a Teflon cap or a semipermeable membrane and stirred for 24 h. The reaction mixture was cooled to room temperature and quenched by addition of 2 ml of water. Dodecane as internal standard was added and after shaking, a small fraction of the organic phase was analysed by GC. The following reaction was investigated. Supplementary Figure S1. Screening reaction of 1-phenylethanol with 2-amino-1-butanol ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

3 Supplementary Table S1. Base Screening Base Yield [%] KO t Bu 55 KOH 32 K(SiMe 3 ) 2 0 KOSiMe 3 0 K 3 PO 4 4 KH 47 K 2 CO 3 0 KOAc 0 ao t Bu 37 ah 2 25 aoac 0 a 2 CO 3 0 LiH 0 Li t Bu 12 Mg(O(C 2 H 5 )) 2 0 Reaction conditions: 1.0 eq. 1-phenylethanol (120 µl), 1.1 eq. 2-amino-1-butanol (104 µl), 1.1 eq. base, 3.0 ml THF, 1 mol% catalyst I, 24 h, 110 C (reaction tubes closed with Teflon caps). Yields determined by GC analyses with dodecane as internal standard. Supplementary Table S2. Solvent Screening Solvent Yield [%] THF 55 DME 54 toluene 41 hexane 49 DMSO 0 diglyme 45 dioxane 48 Reaction conditions: 1.0 eq. 1-phenylethanol (120 µl), 1.1 eq. 2-amino-1-butanol (104 µl), 1.1 eq. KO t Bu, 3.0 ml solvent, 1 mol% catalyst I, 24 h, 110 C (reaction tubes closed with Teflon caps). Yields determined by GC analyses with dodecane as internal standard. Supplementary Table S3. Amount of KO t Bu Base Amount According to Secondary Alcohol [eq.] Yield [%] without base 0 Reaction conditions: 1.0 eq. 1-phenylethanol (120 µl), 1.1 eq. 2-amino-1-butanol (104 µl), 3.0 ml solvent, KO t Bu, 1 mol% catalyst I, 24 h, 110 C (reaction tubes closed with Teflon caps). Yields determined by GC analyses with dodecane as internal standard. Supplementary Table S4. Alcohol Ratio Amino Alcohol /Secondary Alcohol [eq.] Yield [%] 3.0 / / ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

4 1.1 / / / / / / Reaction conditions: 1.1 mmol KO t Bu, 3.0 ml THF, 1 mol% catalyst I, 24 h, 110 C (reaction tubes closed with Teflon caps). Yields determined by GC analyses with dodecane as internal standard. Supplementary Table S5. Solvent Amount Solvent Amount [ml] Yield [%] Reaction conditions: 2.0 eq. 1-phenylethanol (240 µl), 1.0 eq. 2-amino-1-butanol (96 µl) 1.1eq. KO t Bu, 1 mol% catalyst I, 24 h, 110 C (reaction tubes closed with Teflon caps). Yields determined by GC analyses with dodecane as internal standard. Supplementary Table S6. Temperature Screening Temperature [ C] Oil Bath Yield [%] Reaction conditions: 2.0 eq. 1-phenylethanol (240 µl), 1.0 eq. 2-amino-1-butanol (96 µl) 1.1 eq. KO t Bu, 1 mol% catalyst I, 24 h (reaction tubes closed with Teflon caps). Yields determined by GC analyses with dodecane as internal standard. Supplementary Table S7. Catalyst Loading Cat. Loading [mol%] Yield [%] Reaction conditions: 2.0 eq. 1-phenylethanol (240 µl), 1.0 eq. 2-amino-1-butanol (96 µl) 1,1eq. KO t Bu, catalyst I, 24 h, 110 C (reaction tubes closed with Teflon caps). Yields determined by GC analyses with dodecane as internal standard. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

5 Supplementary Table S8. Iridium Catalyst Screening Catalyst Yield [%] I 10 II 63 III 33 IV 54 V [IrOMe(cod)] 2 2 VI [IrCl(cod)] 2 3 Reaction conditions: 2.0 eq. 1-phenylethanol (2.4 ml), 1.0 eq. 2-amino-1-butanol (0.96 ml) 1.1eq. KO t Bu (1.24 g), 0.01 mol% catalyst ( 1.0 ml, M in THF), 10.0 ml THF, 24 h, 90 C (reaction tubes closed with a semipermeable membrane, for more details please see Supplementary Figure S2, next page). Yields determined by GC analyses with dodecane as internal standard. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

6 Supplementary Figure S2: Reaction flask with a semi-permeable membrane as used for the pyrrole syntheses. A silicone tube (Rotilabo ) inner diameter 7 mm, outer diameter 10 mm and 30 cm length was used as membrane. A maximum reaction temperature of 90 C was determined inside the reaction flask due to a pressure increase (1 bar overpressure) caused by the membrane. There are a few reasons for using the semi-permeable membrane. 1. low boiling substrates and 2. low boiling solvents which essentially means more solvent flexibility. Low boiling solvents are especially attractive in the work-up procedures since the solvent can be removed easily (also in the presence of products with rather low boiling points). Furthermore, a rather high throughput can be accomplished. One can easily run 60 flasks in a parallel fashion in a rather small fume hood. As a minor drawback the semi-permeable membrane means essentially adding a short rubber tube on top of the reaction flask. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

7 Ligand and Complex Syntheses Supplementary Figure S3: Ligand and complex syntheses Synthesis of PyHP(iPr) 2 2-Aminopyridine (20.0 mmol, 1.88 g) was dissolved in 100 ml THF and triethylamine (20.0 mmol, 2.8 ml) was added and the solution was cooled to 0 C. Then chlorodiisopropylphosphine (20.0 mmol, 3.2 ml) was added drop wise with a syringe. The solution was allowed to warm to room temperature and stirred over night at 50 C. The suspension was filtered over a glass filter frit with a pad of celite (4 cm) and washed with 50 ml of THF. The solvent was concentrated in vacuo to 10 ml and left to crystallize at -20 C. The supernatant solution was decanted and the solid washed with 5 ml of cold hexane and subsequently dried in vacuo yielding PyHP(iPr) 2 as a colorless solid (19.2 mmol = 96%). 1 H MR (400 MHz, C 6 D 6, 298 K): δ = 8.18 (ddd, J = 4.9, 1.8, 0.9 Hz, 1H), (m, 1H), 7.10 (ddd, J = 8.5, 7.2, 1.7 Hz, 1H), 6.37 (ddd, J = 7.3, 7.1, 0.9 Hz, 1H), 4.86 (d, J = 10.6 Hz, 1H), (m, 2H), (m, 12H) ppm. 13 C MR (100 MHz, C 6 D 6, 298 K): δ = (d, J = 20.0 Hz), (d, J = 1.2 Hz), (d, J = 2.3 Hz), 114.5, (d, J = 18.6 Hz), 26.5 (d, J = 11.6 Hz), 18.7 (d, J = 20.4 Hz), 17.1 (d, J = 8.0 Hz) ppm. 31 P MR (161 MHz, C 6 D 6, 298 K): δ = ppm. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

8 Synthesis of [(PyP(iPr) 2 )Ir(cod)] (Cat. I) PyHP(iPr) 2 (2.0 mmol, 420 mg) was dissolved in 20 ml THF, cooled to -30 C and n-buli (2.0 mmol, 1.6 M, 1.25 ml) was added drop wise with a syringe. The reaction mixture was stirred at -30 C for 30 min and was then allowed to warm to room temperature and stirred for 1h. Then the reaction mixture was added to a solution of [IrCl(cod)] 2 (1.0 mmol, 671 mg) (with a flexible tube). The reaction mixture was stirred for 30 min at room temperature before the solvent was removed in vacuo. The residue was suspended in diethyl ether and filtered over a glass filter frit with a pad of celite (1 cm) and washed with 10 ml of cold diethyl ether. Solvent was removed in vacuo and the residue was recrystallized from hexane affording dark red crystals (1.6 mmol, 80%). 1 H MR (400 MHz, C 6 D 6, 298 K): δ = 7.30 (d, J = 8.8 Hz, 1H), 7.20 (d, J = 6.4 Hz, 1H), (m, 1H), 5.65 (t, J = 6.4 Hz, 1H), (m, 2H), (m, 2H), (m, 4H), (m, 4H), (m, 2H), 1.23 (dd, J = 13.9, 7.0 Hz, 6H), 1.07 (dd, J = 13.9, 7.0 Hz, 6H) ppm. 13 C MR (100 MHz, C 6 D 6, 298 K): δ = (d, J = 2.9 Hz), (d, J = 2.5 Hz), (d, J = 22.5 Hz,) 105.9, 88.3 (d, J = 11.3 Hz), 56.14, 34.4, (d, J = 2.3 Hz), 29.2 (d, J = 1.6 Hz), (d, J = 38.9 Hz), 17.9 (d, J = 3.5 Hz), 17.5 ppm. 31 P MR (161 MHz, C 6 D 6, 298 K): δ = ppm. elemental analysis calcd (%) for C 27 H 32 Ir 2 P: C 44.78, H 5.93, 5.50; found: C 44.77, H 5.68, Synthesis of (4-Ph)Tr(HP(iPr) 2 ) 2 Benzoguanamine (30.0 mmol, 5.61 g) was dissolved in 150 ml THF and triethylamine (40.0 mmol, 2.8 ml) was added and the solution was cooled to 0 C. Then chlorodiisopropylphosphine (60.0 mmol, 9.6 ml) was added drop wise with a syringe. The ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

9 solution was allowed to warm to room temperature and stirred over night at 50 C. The suspension was filtered over a glass filter frit with a pad of celite (4 cm) and washed with 50 ml of THF. The solvent was concentrated in vacuo, recrystallized in toluene yielding (4- Ph)Tr(HP(iPr) 2 ) 2 as colorless crystals (12.06 g = 28.8 mmol = 96%). 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (m, 2H), (m, 3H), 5.25 (s_br, 2H), (m, 4H), (m, 24H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 171.7, (d, J = 12.7 Hz), 137.4, 132.0, 128.9, 128.8, 26.8 (d, J = 14.4 Hz), 19.2 (d, J = 21.0 Hz), 18.0 (d, J = 9.3 Hz) ppm. 31 P MR (161 MHz, C 6 D 6, 298 K): δ = 52.69, ppm. 31 P MR (161 MHz, C 6 D 6, 353 K): δ = ppm. elemental analysis: for C 21 H 35 5 P 2 : C 60.13, H 8.41, 16.70; found: C 60.12, H 8.13, Synthesis of [(4-Ph)Tr(P(iPr) 2 )(HP(iPr) 2 )Ir(cod)] (Cat. II) [IrOMe(cod)] 2 (2.0 mmol, 1.32g) was dissolved in 40 ml THF and subsequently a solution of (4-Ph)Tr(HP(iPr) 2 ) 2 (4.0 mmol, 1.67 g) dissolved in THF was added drop wise. A red solution was obtained. The solution was stirred over night at 50 C. The solvent was removed in vacuo, yielding a deep red solid in quantitative yield. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (m, 2H), (m, 3H), 6.06 (s_br, 1H), (m, 2H), 3.89 (s_br, 2H), (m, 10H), (m, 2H), (m, 24H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = (t, J = 2.2 Hz), 137.9, 131.6, 130.7, 129.1, 128.7, 55.0, 37.0 (t, J = 3.3 Hz), 32.5, 28.5 (s_br), 18.0 (s_br), 16.9 ppm. 31 P MR (161 MHz, C 6 D 6, 298 K): δ = 83.34, ppm. elemental analysis (%) for C 29 H 46 Ir 5 P 2 calcd: C 48.45, H 6.45, 9.74; found: C 48.77, H 6.44, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

10 Synthesis of Py(HP(iPr) 2 ) 2 2,6-Diaminopyridine (30.0 mmol, 3.24 g) was dissolved in 150 ml THF and triethylamine (40.0 mmol, 2.8 ml) was added and the solution was cooled to 0 C. Then chlorodiisopropylphosphine (60.0 mmol, 9.6 ml) was added drop wise with a syringe. The solution was allowed to warm to room temperature and stirred over night at 50 C. The suspension was filtered over a glass filter frit with a pad of celite (4 cm) and washed with 50 ml of THF. The solvent was concentrated in vacuo, recrystallized in hexane yielding Py(HP(iPr) 2 ) 2 as colorless crystals (6.14g = 18.0 mmol = 60%). 1 H MR (400 MHz, C 6 D 6 ): δ = 7.20 (t, J = 7.9 Hz, 1H), 6.72 (dd, J = 7.9, 1.8 Hz, 2H), 4.48 (d, J = 9.6 Hz, 2H), (m, 4H), (m, 24 H) ppm. 13 C MR (75 MHz, CD 2 Cl 2, 298 K): δ = 159,6 (d, J = 20.5 Hz), 140.1, 98.6 (d, J = 18.2Hz), 26.9 (d, J = 11.6 Hz), 19.0 (d, J = 19.9 Hz), 17.4 (d, J = 8.3 Hz) ppm. 31 P MR (161 MHz, C 6 D 6, 298 K): δ = 52.40, ppm. 31 P MR (161 MHz, C 6 D 6, 353 K): δ = ppm. Synthesis of [Py(P(iPr) 2 )(HP(iPr) 2 )Ir(cod)] (Cat. III) [IrOMe(cod)] 2 (1.0 mmol, 662 mg) was dissolved in 20 ml THF and subsequently a solution of Py(HP(iPr) 2 ) 2 (2.0 mmol, 682 mg) dissolved in THF was added drop wise. A red solution was obtained. The solution was stirred over night at 50 C. The solvent was removed in vacuo, yielding a deep red solid in quantitative yield. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 6.87 (tt, J = 7.9, 1.6 Hz, 1H), 5.77 (s_br, 2H), 5.64 (t, J = 4.1 Hz, 2 H), 4.84 (s_br, 1H), (m, 2 H), (m, 2H), (m, 4H), (m, 6H), (m, 2 H), (m, 24 H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 138.7(t, J = 2.2 Hz), 130.8, 51.9, 37.2 (t, J = 3.9 Hz), 32.5, 30.0 (t, J = 16.5 Hz), 18.2( t, J = 2.2 Hz), 16.8 ppm. 31 P MR (161 MHz, C 6 D 6, 298 K): δ = ppm. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

11 elemental analysis (%) for C 25 H 44 Ir 3 P 2 calcd: C 46.86, H 6.92, 6.56; found: C 46.98, H 6.89, Synthesis of (4-Me)Tr(HP(iPr) 2 ) 2 6-Methyl-[1,3,5]triazine-2,4-diamine (30.0 mmol, 3.75 g) was dissolved in 150 ml THF and triethylamine (40.0 mmol, 2.8 ml) was added and the solution was cooled to 0 C. Then chlorodiisopropylphosphine (60.0 mmol, 9.6 ml) was added drop wise with a syringe. The solution was allowed to warm to room temperature and stirred over night at 50 C. The suspension was filtered over a glass filter frit with a pad of celite (4 cm) and washed with 50 ml of THF. The solvent was concentrated in vacuo, recrystallized in toluene yielding (4- Me)Tr(HP(iPr) 2 ) 2 as white crystals (12.06g = 28.8 mmol = 96%). 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 5.11 (s_br, 2H), 2.23 (s, 3H), (m, 4H), (m, 24H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 176.3, (d, J = 13.2 Hz), 46.2, 26.6 (d, J = 14.4 Hz), 19.0 (d, J = 21.0 Hz), 17.9 (d, J = 8.9 Hz) ppm. elemental analysis (%) for C 16 H 33 5 P 2 calcd: C 53.77, H 9.31, 19.59; found: C 53.75, H 9.51, P MR (161 MHz, C 6 D 6, 298 K): δ = 52.13, ppm. 31 P MR (161 MHz, C 6 D 6, 353 K): δ = ppm. Synthesis of [(4-Me)Tr(P(iPr) 2 )(HP(iPr) 2 )Ir(cod)] (Cat. IV) [IrOMe(cod)] 2 (0.5 mmol, 332 mg) was dissolved in 40 ml THF and subsequently a solution of (4-Me)Tr(HP(iPr) 2 ) 2 (1.0 mmol, 357 mg) dissolved in THF was added drop wise. A red solution was obtained. The solution was stirred over night at 50 C. The solvent was removed in vacuo, yielding a deep red solid in quantitative yield. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

12 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 6.87 (tt, J = 7.9, 1.6 Hz, 1H), 5.77 (s_br, 2H), 5.64 (t, J = 4.1 Hz, 2 H), 4.84 (s_br, 1H), (m, 2 H), (m, 2H), (m, 4H), (m, 6H), (m, 2 H), (m, 24 H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 138.7, 130.8, 51.9, 37.2 (t, J = 3.9 Hz), 32.5, 30.0 (t, J = 16.5 Hz), 18.2( t, J = 2.2 Hz), 16.8 ppm. elemental analysis (%) for C 24 H 44 Ir 5 P 2 calcd: C 43.89, H 6.75, 10.66; found: C 43.86, H 6.52, P MR (161 MHz, C 6 D 6, 298 K): δ = 84.54, ppm. Reaction of 1-Phenylethanol with various Amino Alcohols Supplementary Table S9: Reaction of 1-phenylethanol with various amino alcohols OH + HO R = aryl, alkyl R H 2 Cat. II 1.1 eq. KO t Bu, 24h, 90 C H R [mol% Cat. II] Product Yield [a] 1a % 1b % 1c % 1d % 1e % ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

13 1f % 1g % 1h % [a] Isolated yield 1a: 2-methyl-5-phenyl-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), 1-phenylethanol (2.4 ml, 20.0 mmol), 2-amino-propan-1-ol (797 µl, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 40:1 10:1 pentane : Et 2 O; Yield: 1.26 g = 8.0 mmol = 80% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.24 (s_br, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), 2.32 (s, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 133.5, 131.0, 129.7, 129.4, 126.1, 123.6, 108.4, 106.7, 13.4 ppm. MS (70 ev, EI); m/z (%): 157 (65, M + ), 156 (100), 104 (2), 77 (5). elemental analysis (%) for C 11 H 11 calcd C 84.04, H 7.05, 8.91; found: C H b: 2-ethyl-5-phenyl-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), 1- phenylethanol (2.4 ml, 20.0 mmol), 2-amino-butan-1-ol (960 µl, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 40:1 pentane: Et 2 O; Yield: 1.59 g = 9.3 mmol = 93% as colorless solid. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

14 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.23 (s_br, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), 2.68 (q, J = 7.6 Hz, 2H), 1.27 (t, J = 7.6 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 136.3, 133.6, 130.8, 129.4, 126.1, 123.7, 106.7, 21.5, 14.1 ppm. MS (70 ev, EI); m/z (%): 171 (38, M + ), 156 (100), 128 (8), 115 (6), 77 (5). elemental analysis (%) for C 12 H 13 calcd: C 84.17, H 7.65, 8.18; found: C 84.33, H 7.69, c: 3-(5-phenyl-1H-pyrrol-2-ylmethyl)-1H-indole: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), 1-phenylethanol (2.4 ml, 20.0 mmol), 2-amino-3-(1H-indol-3-yl)-propan-1-ol (1.90 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 20:1 10:1 pentane : Et 2 O;Yield: 1.76 g = 6.5 mmol = 65% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.24 (s_br, 1H), 8.16 (s_br, 1H), (m, 1H), (m, 3H), (m, 2H), (m, 4H), (m, 1H), (m, 1H), 4.16 (s, 2H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 137.1, 133.5, 133.3, 131.2, 129.3, 127.8, 126.1, 123.7, 123.0, 122.7, 120.0, 119.3, 114.1, 111.7, 108.2, 106.6, 24.5 ppm. MS (70 ev, EI); m/z (%): 272 (100, M + ), 270 (10), 167 (10), 136 (10), 117 (38), 77 (8). elemental analysis (%) for C 19 H 16 2 calcd: C 83.79, H 5.92, 10.29; found: C 83.62, H 5.98, d: 2-isopropyl-5-phenyl-1H-pyrrole: Cat. II (0.3 ml, mmol, 0.01 M in THF), 1- phenylethanol (2.4 ml, 20.0 mmol), 2-amino-3-methyl-butan-1-ol (1.03 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 100:1 30:1 pentane : Et 2 O; Yield: 1.64 g = 8.9 mmol = 89% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.23 (s_br, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 1.30 (d, J = 6.7 Hz, 6H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 141.0, 133.6, 130.7, 129.4, 126.1, 123.8, 106.4, 105.5, 27.8, 23.1 ppm. MS (70 ev, EI); m/z (%): 185 (28, M + ), 170 (100), 153 (5), 115 (8), 77 (5). ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

15 elemental analysis (%) for C 13 H 15 calcd: C 84.28, H 8.16, 7.56; found: C 84.46, H 8.23, e: 2-sec-butyl-5-phenyl-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), 1-phenylethanol (2.4 ml, 20.0 mmol), 2-amino-3-methyl-pentan-1-ol (1.17 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 30:1 pentane : Et 2 O; Yield: 1.84 g = 7.9 mmol = 79% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (s_br, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), (m, 3H), (m, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 139.9, 133.6, 130.5, 129.3, 126.1, 123.7, 106.4, 106.2, 35.0, 30.8, 20.5, 12.2 ppm. MS (70 ev, EI); m/z (%): 199 (22, M + ), 184 (8), 170 (100), 168 (10), 115 (6), 77 (5). elemental analysis (%) for C 14 H 17 calcd C 84.37, H 8.60, 7.03; found: C 84.66, H 8.89, f: 2-isobutyl-5-phenyl-1H-pyrrole: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), 1-phenylethanol (2.4 ml, 20.0 mmol), 2-amino-4-methyl-pentan-1-ol (1.28 ml, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 20:1 pentane : Et 2 O; Yield: 1.39 g = 6.9 mmol = 69% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.19 (s_br, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), 2.50 (d, J = 7.0 Hz), (m, 1H), 0.96 (d, J = 6.7 Hz, 6H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 133.9, 133.6, 130.7, 129.4, 126.0, 123.6, 108.5, 106.6, 37.8, 29.8, 22.7 ppm. MS (70 ev, EI); m/z (%): 199 (18, M + ), 156 (100), 115 (5), 77 (5). elemental analysis (%) for C 14 H 17 calcd C 84.37, H 8.60, 7.03; found: C 84.46, H 8.50, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

16 1g: 2,5-diphenyl-1H-pyrrole: Cat. II (2.0 ml, 0.02 mmol, 0.01 M in THF), 1-phenylethanol (2.4 ml, 20.0 mmol), 2-amino-2-phenyl-ethanol (1.37 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 10:1 5:1 hexane : Et 2 O; Yield: 1.88 g = 8.6 mmol = 86% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.72 (s_br, 1H), (m, 4H), (m, 4H), (m, 2H), 6.59 (d, J = 2.6 Hz, 2H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 133.0, 129.5, 127.3, 127.0, 124.2, ppm. MS (70 ev, EI); m/z (%): 219 (100, M + ), 216 (14), 114 (24), 109 (12), 77 (4). elemental analysis (%) for C 16 H 13 calcd: C 87.64, H 5.98, 6.39; found: C H h: 2-benzyl-5-phenyl-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), 1-phenylethanol (2.4 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 40:1 5:1 pentane : Et 2 O; Yield: 1.84 g = 7.9 mmol = 79% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.18 (s_br, 1H), (m, 2H), (m, 4H), (m, 3H), (m, 1H), (m, 1H), (m, 1H), 4.02 (s, 2H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.2, 133.4, 132.9, 129.3, 129.2, 129.1, 127.0, 126.3, 123.8, 109.0, 106.6, 34.7 ppm. MS (70 ev, EI); m/z (%): 233 (84, M + ), 156 (100), 128 (15), 115 (8), 77 (6). elemental analysis (%) for C 17 H 15 calcd: C 87.52, H 6.48, 6.00; found: C 87.62, H 6.21, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

17 Reaction of 2-Amino-3-phenyl-propan-1-ol with various Secondary Alcohols Supplementary Table S10. Reaction of 2-amino-3-phenyl-propan-1-ol with various secondary alcohols OH HO + Cat. II R H 1.1 eq. KO t H 2 Bu, 24h, 90 C R = aryl, alkyl R [mol% Cat. II] Product Yield [a] 1i % 1j % 1k % 1l % 1m % 1n % 1o % ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

18 1p % 1q % 1r % 1s % 1t % 1u % 1v % [a] Isolated yield ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

19 1i: 2-benzyl-5-methyl-1H-pyrrole: Cat. II (0.3 ml, mmol, 0.01 M in THF), propan-2-ol (3.06 ml, 40.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 20:1 pentane : Et 2 O; Yield: 1.43 g = 8.4 mmol = 85% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.59 (s_br, 1H), (m, 2H), (m, 3H), 5.79 (t, J = 2.9 Hz, 1H), (m, 1H), 3.90(s, 2H), 2.18 (s, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.9, 129.8, 129.0, 127.4, 126.8, 106.9, 106.2, 34.7, 13.2 ppm. MS (70 ev, EI); m/z (%): 171 (100, M + ), 156 (72), 154 (18), 128 (8), 94 (100), 77 (8). elemental analysis (%) for C 12 H 13 calcd: C 84.17, H 7.65, 8.18; found: C 84.20, H 7.86, j: 2-benzyl-5-butyl-1H-pyrrole: Cat. II (0.3 ml, mmol, 0.01 M in THF), hexan-2-ol (2.52 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 40:1 30:1 pentane : Et 2 O; Yield: 1.62 g = 7.6 mmol = 76% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.61 (s_br, 1H), (m, 2H), (m, 3H), (m, 1H), (m, 1H), 3.92 (s, 2H), (m, 2H), (m, 2H), (m, 2H), 0.92 (t, J = 7.3 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.9, 132.7, 129.5, 129.1, 129.0, 126.7, 106.8, 105.2, 34.7, 32.5, 27.9, 23.0, 14.2 ppm. MS (70 ev, EI); m/z (%): 213 (60, M + ), 198 (20), 184 (100), 170 (35), 155 (10), 128 (6), 84 (4), 77 (6). elemental analysis (%) for C 15 H 19 calcd: C 84.46, H 8.98, 6.57; found: C H k: 2-benzyl-5-hexyl-1H-pyrrole: Cat. II (0.3 ml, mmol, 0.01 M in THF), octan-2-ol (3.1 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 20:1 10:1 pentane : Et 2 O; Yield: 2.34 g = 9.7 mmol = 97% as colorless oil. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

20 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.60 (s_br, 1H), (m, 2H), (m, 3H), (m, 1H), (m, 1H), 3.90 (s, 2H), (m, 2H), (m, 2H), (m, 6H), (m, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.9, 132.8, 129.5, 129.1, 126.7, 107.5, 106.8, 105.2, 34.7, 32.2, 30.3, 29.6, 28.3, 23.2, 14.4 ppm. MS (70 ev, EI); m/z (%): 241 (18, M + ), 170 (100), 167 (4), 93 (4), 91 (7), 80 (5). elemental analysis (%) for C 17 H 23 calcd: C 84.59, H 9.60, 5.80; found: C 84.28, H 9.86, l: 2-benzyl-5-nonyl-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), undecan-2-ol (4.16 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 40:1 pentane : Et 2 O; Yield: 2.09 g = 7.4 mmol = 74% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.60 (s_br, 1H), (m, 2H), (m, 3H), (m, 1H), (m, 1H), 3.91 (s, 2H), (m, 2H), (m, 2H), (m, 12H), (m, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.9, 132.8, 129.5, 129.1, 129.0, 126.7, 106.7, 105.2, 34.7, 32.5, 30.4, 30.1, 30.0, 30.0, 29.9, 28.3, 23.3, 14.5 ppm. MS (70 ev, EI); m/z (%): 283 (21, M + ), 184 (8), 170 (100), 156 (3), 106 (4), 91 (8), 80 (4). elemental analysis (%) for C 20 H 29 calcd: C 84.75, H 10.31, 4.94; found: C 84.85, H 10.52, m: 2-benzyl-5-(4-methyl-pent-3-enyl)-1H-pyrrole: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), 6-methyl-hept-5-en-2-ol (3.04 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 70:1 40:1 pentane : Et 2 O; Yield: 1.84g = 7.7 mmol = 77% as colorless oil 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.64 (s_br, 1H), (m, 2H), (m, 3H), (m, 1H), (m, 1H), (m, 1H), 3.90 (s, 2H), 2.53 (t, J = 7.3 Hz, 2H), 2.23 (q, J = 7.3 Hz, 2H), 1.66 (d, J = 1.2 Hz, 3H), 1.54 (s, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.9, 133.0, 132.5, 129.7, 129.1, 129.0, 126.8, 124.4, 106.7, 105.4, 34.7, 28.9, 28.3, 26.0, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

21 17.9 ppm. MS (70 ev, EI); m/z (%): 239 (100, M + ), 224 (44), 184 (6), 170 (20), 148 (48), 133 (8), 94 (8), 91 (32). elemental analysis (%) for C 17 H 21 calcd: C 85.30, H 8.84, 5.85; found: C 85.65, H 9.13, n: 2-benzyl-5-isopropyl-1H-pyrrole: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), 3-methylbutan-2-ol (2.15 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 30:1 pentane : Et 2 O; Yield: 1.45 g = 7.3 mmol = 73% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.66 (s_br, 1H), (m, 2H), (m, 3H), (m, 2H), 3.93 (s, 2H), (m, 1H), 1.21 (d, J = 7.0 Hz, 6H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.9, 138.8, 129.5, 129.1, 129.0, 126.7, 106.6, 103.3, 34.7, 27.6, 23.1 ppm. MS (70 ev, EI); m/z (%): 199 (52, M + ), 184 (100), 106 (16), 91 (26). elemental analysis (%) for C 14 H 17 calcd: C 84.37, H 8.60, 7.03; found: C 84.16, H 8.29, o: 2-benzyl-5-(4-methoxy-phenyl)-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), 1-(4-methoxy-phenyl)-ethanol (2.82 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 20:1 5:1 pentane : Et 2 O; Yield: 2.22 g = 8.4 mmol = 84% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.07 (s_br, 1H), (m, 4H), (m, 3H), (m, 2H), , (m, 1H), (m, 1H), 4.00 (s, 2H), 3.79 (s, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 158.6, 140.3, 132.1, 131.8, 129.1, 126.9, 126.4, 125.2, 114.7, 108.8, 105.4, 105.3, 55.8, 34.7 ppm. MS (70 ev, EI); m/z (%): 263 (100, M + ), 248 (31), 219 (5), 186 (38), 143 (10), 102 (8), 77 (6). ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

22 elemental analysis (%) for C 18 H 17 O calcd: C 82.10, H 6.51, 5.32; found: C 81.92, H 6.57, p: 2-benzyl-5-(4-chloro-phenyl)-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), 1-(4-chloro-phenyl)-ethanol (2.67 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 40:1 5:1 pentane : Et 2 O; Yield: 2.02 g = 7.5 mmol = 75% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.14 (s_br, 1H), (m, 9H), (m, 1H), (m, 1H), 4.01 (s, 1H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.0, 133.4, 131.9, 131.5, 130.6, 129.4, 129.2, 129.1, 127.0, 125.0, 109.2, 107.2, 34.7 ppm. MS (70 ev, EI); m/z (%): 267 (100, M + ), 230 (5), 192 (22), 190 (82), 154 (18), 127 (12), 101 (8), 77 (8). elemental analysis (%) for C 17 H 14 Cl calcd: C 76.26, H 5.27, 5.23; found: C 76.26, H 5.43, q: 2-benzyl-5-(4-bromo-phenyl)-1H-pyrrole: Cat. II (2.0 ml, 0.02 mmol, 0.01 M in THF), 1-(4-bromo-phenyl)-ethanol (4.0 g, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 30:1 5:1 pentane : Et 2 O; Yield: 2.35 g = 7.5 mmol = 75% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.15 (s_br, 1H), (m, 2H), (m, 7H), (m, 1H), (m, 1H), 4.00 (s, 2H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.0, 133.5, 132.3, 130.6, 129.2, 129.1, 127.0, 125.3, 123.8, 119.5, 109.3, 107.3, 34.7 ppm. MS (70 ev, EI); m/z (%): 311 (100), 234 (95), 202 (10), 154 (77), 115 (27), 102 (22), 77 (17). elemental analysis (%) for C 17 H 14 Br calcd: C 65.40, H 4.52, 4.49; found C 65.54, H 4.60, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

23 1r: 2-benzyl-5-ferrocenyl-1H-pyrrole: Cat. II (2.0 ml, 0.02 mmol, 0.01 M in THF), 1- ferrocenyl-ethanol (4.6 g, 20.0 mmol) 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 40:1 20:1 pentane : Et 2 O; Yield: 2.67 g = 7.8 mmol = 78% deep red solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.84 (s_br, 1H), (m, 2H), (m, 3H), (m, 1H), (m, 1H), (m, 2H), (m, 2H), 4.02 (s, 5H), 3.98 (s_br, 2H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.6, 130.8, 129.5, 129.1, 129.0, 126.9, 108.1, 105.7, 80.0, 69.7, 68.3, 65.5, 34.6 ppm. MS (70 ev, EI); m/z (%): 341 (100, M + ), 275 (18), 250 (27), 218 (9), 171 (9), 121 (12), 91 (5), 77 (3). elemental analysis (%) for C 21 H 19 Fe calcd: C 73.92, H 5.61, 4.10; found: C 74.19, H 5.77, s: 2-benzyl-5-furan-2-yl-1H-pyrrole: Cat. II (5.0 ml, 0.05 mmol, 0.01 M in THF), 1-furan-2- yl-ethanol (2.1 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 20:1 15:1 pentane : Et 2 O; Yield: 930 mg = 4.2 mmol = 42% as yellow oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.25 (s_br, 1H), (m, 2H), (m, 3H), 6.43 (dd, J = 3.4, 1.9 Hz, 1H), (m, 1H), 6.30 (dd, J = 3.4, 0.7 Hz, 1H), (m, 1H), 4.00 (s, 2H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 149.0, 140.6, 140.1, 132.3, 129.2, 129.1, 127.0, 123.8, 112.0, 108.6, 106.1, 102.1, 34.5 ppm. MS (70 ev, EI); m/z (%): 223 (100, M + ), 146 (100), 117 (7), 91 (14), 77 (6). elemental analysis (%) for C 15 H 13 O calcd: C 80.69, H 5.87, 6.27; found: C 80.60, H 5.94, 6.55 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

24 1t: 2-benzyl-5-thiophen-2-yl-1H-pyrrole: Cat. II (5.0 ml, 0.05 mmol, 0.01 M in THF), 1- thiophen-2-yl-ethanol (2.56 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 20:1 15:1 pentane : Et 2 O; Yield: 1.36 g = 5.7 mmol = 57% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.06 (s_br, 1H), (m, 2H), (m, 3H), 7.11 (dd, J = 5.1, 1.3 Hz, 1H), (m, 2H), (m, 1H), (m, 1H), 3.99 (s, 2H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.0, 137.0, 132.6, 129.2, 129.1, 128.1,127.0, 126.4, 122.7, 120.7, 108.9, 107.3, 34.6 ppm. MS (70 ev, EI); m/z (%): 239 (89, M + ), 204 (6), 162 (100), 102 (6), 91 (7). elemental analysis (%) for C 15 H 13 S calcd: C 75.28, H 5.47, 5.85; found: C 75.06, H 5.50, u: 4-(5-benzyl-1H-pyrrol-2-yl)-butan-2-ol: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), hexane-2,5-diol (2.36 g, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 10.0 mmol), 24 h at 90 C. Purification by column chromatography 2:1 1:1 pentane : Et 2 O; Yield: 1.60 g = 7.0 mmol = 70% as yellow oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.95 (br_s, 1H), (m, 2H), (m, 3H), (m, 2H), 3.90 (s, 2H), (m, 1H), 2.61 (dt, J = 7.7, 2.5 Hz, 1H), (m, 2H), 1.59 (br_s, 1H), 1.18 (d, J = 6.4 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.9, 132.0, 129.9, 129.1, 129.0, 126.7, 106.7, 105.4, 68.1, 39.4, 34.7, 24.6, 24.0 ppm. MS (70 ev, EI); m/z (%): 229 (56, M + ), 184 (100), 170 (75), 156 (6), 128 (5), 106 (15), 91 (30), 80 (14), 65 (18). elemental analysis (%) for C 15 H 19 O calcd: C 78.56, H 8.35, 6.11; found: C 78.78, H 8.64, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

25 1v: 2,2-dimethyl-5-phenyl-2H-pyrrole: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), 1- phenylethanol (2.4 ml, 20.0 mmol), 2-amino-2-methyl-propan-1-ol (1.1 ml, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 40:1 2:1 pentane : Et 2 O; Yield: 0.94 g = 5.5 mmol = 55% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (m, 2H), (m, 3H), 7.41 (d, J = 5.0 Hz, 1H), 6.79 (d, J = 5.0 Hz, 1H), 1.38 (s, 6H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 169.6, 153.0, 135.0, 130.6, 129.1, 128.1, 123.3, 80.0, 23.7 ppm. MS (70 ev, EI); m/z (%): 171 (81, M + ), 170 (100), 156 (37), 129 (12), 104 (18), 77 (12). elemental analysis (%) for C 12 H 13 calcd: C 84.17, H 7.65, 8.18; found: C 84.03, H 7.88, Reaction of 2-Amino-3-phenyl-propan-1-ol with various Cyclic Alcohols Supplementary Table S11: Reaction of 2-amino-3-phenyl-propan-1-ol with various secondary alcohols and cyclic alcohols [mol% Cat. II] Product Yield [a] 2a % 2b % 2c % 2d % 2e % ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

26 2f % 2g % 2h % 2i % 2j % 2k % 2l % [a] Isolated yield 2a: 5-benzyl-3-methyl-2-phenyl-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), 1- phenyl-propan-1-ol (2.74 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 20:1 hexane : Et 2 O; Yield: 1.55 g = 6.2 mmol = 63% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.86 (s_br, 1H), (m, 10H), 5.89 (d, J = 2.9 Hz, 1H), 3.97 (s, 2H), 2.23 (s,3h) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.3, 134.3, 131.3, 129.2, 129.1, 127.7, 127.0, 126.3, 126.0, 116.9, 111.3, 34.6, 12.9 ppm. MS (70 ev, EI); m/z (%): 247 (100, M + ), 232 (47), 170 (83), 128 (6), 115 (11), 77 (6) ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

27 elemental analysis (%) for C 18 H 17 calcd: C 87.41, H 6.93, 5.66; found: C 87.31, H 7.01, b: 5-benzyl-2-ethyl-3-methyl-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), pentan-3-ol (2.16 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 30:1 hexane : Et 2 O; Yield: 1.31 g = 6.6 mmol = 66% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.44 (s_br, 1H), (m, 2H), (m, 3H), 5.67 (d, J = 2.6 Hz, 1H), 3.87 (s, 2H), 2.50 (q, J = 7.6 Hz, 2H), 1.97 (s, 3H), 1.12 (t, J = 7.6 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 129.1, 129.0, 128.3, 126.7, 113.6, 108.8, 34.7, 19.4, 14.9, 11.0 ppm. MS (70 ev, EI); m/z (%): 199 (82, M + ), 184 (100), 169 (25), 107 (9), 91 (25), 77 (8). elemental analysis (%) for C 14 H 17 calcd: C 84.37, H 8.60, 7.03; found: C 84.18, H 8.74, c: 5-benzyl-2-butyl-3-propyl-1H-pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), nonan-5-ol (3.49 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 pentane : Et 2 O; Yield: 1.33 g = 5.2 mmol = 52% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.41 (s_br, 1H), (m, 2H), (m, 3H), 5.69 (d, J = 2.9 Hz, 1H), 3.88 (s, 2H), (m, 2H), (m, 2H), (m, 4H), (m, 2H), (m, 6H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 141.0, 129.1, 129.0, 128.4, 127.9, 126.7, 119.7, 107.4, 34.7, 33.3, 28.6, 25.9, 25.3, 23.1, 14.5, 14.3 ppm. MS (70 ev, EI); m/z (%): 255 (31, M + ), 226 (9), 212 (100), 184 (12), 91 (16) ppm. elemental analysis (%) for C 18 H 25 calcd: C 84.65, H 9.87, 5.48; found: C 84.33, H 10.11, 5.29 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

28 2d: 2-(1H-indol-3-ylmethyl)- 1,5,6,7,8,9-hexahydro-cyclohepta[b]pyrrole: Cat. II (5.0 ml, 0.05 mmol, 0.01 M in THF), cycloheptanol (2.4 ml, 20.0 mmol), 2-amino-3-(1H-indol-3-yl)- propan-1-ol (1.90 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 10:1 2:1 pentane : Et 2 O; Yield: 1.49 g = 5.6 mmol = 56 % as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.07 (s_br, 1H), (m, 1H), 7.46 (s_br, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), 5.74 (d, J = 2.9 Hz, 1H), 4.01 (s, 2H), (m, 4H), (m, 2H), (m, 4H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 137.0, 129.3, 127.9, 127.0, 122.8, 122.5, 121.7, 119.8, 119.4, 114.8, 111.7, 108.2, 32.6, 30.1, 29.6, 29.0, 28.8, 24.0 ppm. MS (70 ev, EI); m/z (%): 264 (100, M + ), 263 (85), 235 (15), 221 (32), 148 (51), 130 (16), 116 (23), 104 (22), 90 (6), 77 (8). elemental analysis (%) for C 18 H 20 2 calcd: C 81.78, H 7.63, 10.60; found: C 82.12, H 7.95, H 2e: 2-methyl-1,5,6,7,8,9-hexahydro-cyclohepta[b]pyrrole: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), cycloheptanol (2.4 ml, 20.0 mmol), 2-amino-propan-1-ol (797 µl, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 20:1 hexane : Et 2 O; Yield: 1.16 g = 7.8 mmol = 78% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.42 (s_br, 1H), 5.57 (d, J = 2.93 Hz, 1H), (m, 2H), (m, 2H), 2.16 (s, 3H), (m, 2H), (m, 4H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 129.1, 123.3, 121.8, 108.5, 32.7, 30.2, 29.6, 28.9, 13.0 ppm. MS (70 ev, EI); m/z (%): 149 (88, M + ), 148 (100), 134 (15), 120 (40), 107 (32), 94 (30), 91 (11), 77 (8). elemental analysis (%) for C 10 H 15 calcd: C 80.48, H 10.13, 9.39; found: C 80.85, H 10.30, 9.65 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

29 2f: 2-ethyl-1,5,6,7,8,9-hexahydro-cyclohepta[b]pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), cycloheptanol (2.4 ml, 20.0 mmol), 2-amino-butan-1-ol (960 µl, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 40:1 20:1 pentane : Et 2 O; Yield: 1.44 g = 8.8 mmol = 88% as yellow oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.45 (s_br, 1H), 5.58 (d, J = 2.9 Hz, 1H), (m, 2H), (m, 4H), (m, 2H), (m, 4H), 1.18 (t, J = 7.6 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 130.1, 128.9, 121.6, 106.9, 32.6, 30.2, 29.6, 29.0, 28.9, 21.2, 14.3 ppm. MS (70 ev, EI); m/z (%): 163 (50, M + ), 148 (100), 134 (26), 106 (10), 77 (8). elemental analysis (%) for C 11 H 17 calcd: C 80.93, H 10.50, 8.58; found: C 80.60, H 10.87, g: 2-isopropyl-1,5,6,7,8,9-hexahydro-cyclohepta[b]pyrrole: Cat. II (0.3 ml, mmol, 0.01 M in THF), cycloheptanol (2.4 ml, 20.0 mmol), 2-amino-3-methyl-butan-1-ol (1.1 ml, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 40:1 pentane : Et 2 O; Yield: 1.49 g = 8.4 mmol = 84% as yellow oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.47 (s_br, 1H), (d, J = 2.9 Hz, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 2H), (m, 4H), 1.20 (t, J = 6.7 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 134.8, 128.7, 121.3, 105.6, 32.6, 30.1, 29.6, 29.0, 28.9, 27.4, 23.2 ppm. MS (70 ev, EI); m/z (%): 177 (15, M + ), 162 (100), 106 (5), 77 (6). elemental analysis (%) for C 12 H 19 calcd: C 81.30, H 10.80, 7.90; found: C 81.40, H 11.14, h: 2-sec-butyl-1,5,6,7,8,9-hexahydro-cyclohepta[b]pyrrole: Cat. II (0.3 ml, mmol, 0.01 M in THF), cycloheptanol (2.4 ml, 20.0 mmol), 2-amino-3-methyl-pentan-1-ol (1.17 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 40:1 pentane : Et 2 O; Yield: 1.52 g = 7.9 mmol = 79 % as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.43 (s_br, 1H), 5.57 (d, J = 2.9 Hz, 1H), (m, 2H), (m, 3H), (m, 2H), (m, 4H), (m, 2H), 1.17 (d, J = 6.7 Hz, 3H), 0.89 (t, J = 7.5 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 133.7, 128.6, 121.2, 106.2, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

30 34.6, 32.6, 30.8, 30.1, 29.7, 29.1, 28.9, 20.5, 12.3 ppm. MS (70 ev, EI); m/z (%): 191 (10, M + ), 176 (7), 162 (100), 132 (4), 106 (3) 77 (2). elemental analysis (%) for C 13 H 21 calcd: C 81.61, H 11.06, 7.32; found: C 81.74, H 11.19, i: 2-benzyl-1,5,6,7,8,9-hexahydro-cyclohepta[b]pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), cycloheptanol (2.4 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 30:1 10:1 pentane : Et 2 O; Yield: 1.82 g = 8.0 mmol = 80% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.40 (s_br, 1H), (m, 2H), (m, 3H), 5.65 (d, J = 2.9 Hz, 1H), 3.84 (s, 2H), (m, 2H), (m, 2H), (m, 2H), (m, 4H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 141.0, 129.9, 129.1, 129.0, 126.8, 126.7, 121.8, 108.9, 34.6, 32.6, 30.1, 29.6, 28.9, 28.8 ppm. MS (70 ev, EI); m/z (%): 225 (100, M + ), 196 (28), 148 (20), 134 (30), 91 (40), 77 (10). elemental analysis (%) for C 16 H 19 calcd: C 85.28, H 8.50, 6.22; found: C 85.24, H 8.71, j: 2-benzyl-1,5,6,7-tetrahydro-cyclopenta[b]pyrrole: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), cyclopentanol (1.82 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 30:1 20:1 pentane : Et 2 O; Yield: 999 mg = 5.1 mmol = 51% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.53 (s_br, 1H), (m, 2H), (m, 3H), 5.71 (d, J = 1.8 Hz, 1H), (m, 4H), (m, 2H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 141.0, 135.9, 134.2, 129.1, 126.8, 126.7, 102.6, 35.4, 29.5, 26.1, 25.9 ppm. MS (70 ev, EI); m/z (%): 197 (93, M + ), 196 (100), 182 (10), 169 (25), 152 (5), 120 (81), 106 (22), 91 (34), 85 (15), 77 (13). elemental analysis (%) for C 14 H 15 calcd: C 85.24, H 7.66, 7.10; found: C 85.55, H 7.79, 6.97 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

31 2k: 2-benzyl-5,6,7,8,9,10-hexahydro-1H-cycloocta[b]pyrrole: Cat. II (0.5 ml, mmol, 0.01 M in THF), cyclooctanol (2.64 ml, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 40:1 20:1 pentane : Et 2 O; Yield: 1.85 g = 7.7 mmol = 77% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.41 (s_br, 1H), (m, 2H), (m, 3H), 5.66 (d, J = 2.9 Hz, 1H), (m, 2H), (m, 2H), (m, 2H), (m, 4H), (m, 4H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 141.1, 129.1, 129.0, 128.1, 127.7, 126.6, 119.5, 108.0, 34.7, 31.3, 30.3, 26.6, 26.3, 25.9, 25.5 ppm. MS (70 ev, EI); m/z (%): 239 (100, M + ), 210 (62), 196 (45), 148 (35), 118 (10), 91 (52). elemental analysis (%) for C 16 H 19 calcd: C 85.30, H 8.84, 5.85; found: C 85.66, H 8.92, l: 2-benzyl-5,6,7,8,9,10,11,12,13,14-decahydro-1H-cyclododeca[b]pyrrole: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), cyclododecanol (3.68 g, 20.0 mmol), 2-amino-3-phenyl-propan-1- ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 60:1 40:1 hexane : Et 2 O; Yield: 1.1 g = 3.74 mmol = 37% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.37 (s_br, 1H), (m, 2H), (m, 3H), 5.68 (d, J = 2.9 Hz, 1H), 3.88 (s, 2H), 2.51 (t, J = 6.9 Hz, 2H), 2.36 (t, J = 6.9 Hz, 2H), 1.63 (m, 4H), (m, 8H), (m, 4H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 141.0, 129.4, 129.1, 129.0, 128.1, 126.7, 120.5, 107.0, 34.8, 29.6, 28.6, 25.4, 25.2, 25.1, 25.0, 23.0, 22.9, 22.8, 22.5 ppm. MS (70 ev, EI); m/z (%): 295 (100, M + ), 266 (7), 252 (14), 238 (12), 210 (30), 204 (35), 196 (40), 184 (38), 171 (40), 91 (40). elemental analysis (%) for C 21 H 29 calcd: C 85.37, H 9.89, 4.74; found: C 85.11, H 10.11, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

32 Reaction of Hexane-2,5-diol with various Amino Alcohols to Symmetric and Unsymmetric Bipyrroles Supplementary Table S12: Reaction of hexane-2,5-diol with various amino alcohols to symmetric and unsymmetric bipyrroles [mol% Cat. II] Product Yield [a] 3a % 3b % [a] Isolated yield 3a: 1,2-bis(5-benzyl-1H-pyrrol-2-yl)ethane: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), hexane-2,5-diol (1.18 g, 10.0 mmol), 2-amino-3-phenyl-propan-1-ol (6.04 g, 40.0 mmol), 20 ml THF, KO t Bu (2.48 g, 22.0 mmol), 24 h at 90 C. Purification by column chromatography 8:1 4:1 pentane : Et 2 O; Yield: 1.43 g = 4.2 mmol = 42% as colorless solid. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

33 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.55 (s_br, 2H), (m, 4H), (m, 6H), (m, 4H), 3.86 (s, 4H), 2.77 (s, 4H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.7, 131.7, 130.0, 129.0, 126.8, 106.7, 105.8, 34.6, 28.5 ppm. MS (70 ev, EI); m/z (%): 340 (2, M + ), 325 (2), 249 (50), 183 (60), 170 (100), 156 (28), 91 (30). elemental analysis (%) for C 24 H 24 2 calcd: C 84.67, H 7.11, 8.23; found: C 84.42, H 7.17, b: 2-benzyl-5-(2-(5-ethyl-1H-pyrrol-2-yl)ethyl)-1H-pyrrole: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), 4-(5-benzyl-1H-pyrrol-2-yl)-butan-2-ol (4.584 g, 20.0 mmol), 2-amino-1- butanol (960 µl, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 8:1 4:1 pentane : Et 2 O; Yield: 2.31 g = 8.3 mmol = 83% as yellow oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.58 (s_br, 1H), (m, 2H), (m, 3H), (m, 2H), (m, 2H), 3.89 (s, 2H), 2.81 (s, 4H), 2.53 (q, J = 7.6 Hz, 2H), 1.20 (t, J = 7.6 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 140.7, 133.4, 131.9, 130.7, 130.1, 129.1, 129.0, 126.8, 106.7, 105.7, 105.6, 104.4, 34.7, 28.7, 28.6, 21.3, 14.2 ppm. MS (70 ev, EI); m/z (%): 278 (2, M + ), 186 (1), 170 (100), 108 (75), 93 (12). elemental analysis (%) for C 19 H 22 2 calcd: C 81.97, H 7.97, 10,06; found: C 81.83, H 8.25, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

34 Syntheses of -protected Amino Alcohols and their Conversion with 2-Amino-3-phenyl-propan-1-ol Supplementary Table S13: Syntheses of -protected amino alcohols and their conversion with 2-amino-3-phenylpropan-1-ol R 1 R 1 X X X= CH, H H 2 + OH R 2 + HO HO R 2 OH R 3 H 2 cat. II KO t Bu cat. II 1.1 eq. KO t Bu, 24h, 90 C [mol% Cat. II] Product Yield [a] R 1 R 1 X X H H R 2 OH R 2 H R % 3c % % 3d % ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

35 0.3 89% 3e % [a] Isolated yield 1-(phenylamino)propan-2-ol: Cat. II (0.4 mmol, 288 mg), aniline (7.28 ml, 80.0 mmol) propane-1,2-diol (23.6 ml, mmol), 60 ml THF, KO t Bu (9.04 g, 80.0 mmol), 24 h at 110 C. Purification by HV distillation (3.0x 10-2 mbar, 96 C) 11.11g = 73.5 mmol = 92% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (m, 2H), (m, 3H), 4.05 (s_br, 1H), (m, 1H), 3.20 (d, J = 12.6 Hz, 1H), 2.97 (dd, J = 12.6, 8.6 Hz, 1H), 2.21 (s_br, 1H), 1.24 (d, J = 6.4 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ =149.1, 129.7, 118.0, 113.6, 66.9, 52.1, 21.3 ppm. 3c: 5-benzyl-2-methyl--phenyl-1H-pyrrol-3-amine: Cat. II (1.0 ml, 0.01 mmol, 0.01 M in THF), 1-phenylamino-propan-2-ol (3.02 g, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 2:1 1:1 pentane : Et 2 O; Yield: 2.17 g = 8.3 mmol = 83% as deep red oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.51 (s_br, 1H), (m, 2H), (m, 3H), (m, 2H), (m, 3H), 5.82 (d, J = 2.9 Hz, 1H), 5.00 (s_br, 1H), 3.91 (s, 2H), 2.07 (s, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 149.2, 141.5, 129.6, , , 128.1, 126.9, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

36 122.0, 121.8, 117.6, 113.5, 105.6, 34.9, 10.6 ppm. MS (70 ev, EI); m/z (%): 262 (12, M + ), 217 (8), 185 (100), 169 (60), 143 (16), 131 (17), 115 (35), 104 (14), 91 (38), 77 (22). elemental analysis (%) for C 18 H 18 2 calcd: C 82.41, H 6.92, 10.68; found: C 82.22, H 6.71, (phenylamino)hexan-2-ol: Cat. II (0.4 mmol, 288 mg), aniline (7.28 ml, 80.0 mmol), hexane-1,2-diol (24.8 ml, mmol), 40 ml THF, KO t Bu (9.94 g, 88.0 mmol), 72 h at 110 C. Purification by HV distillation ( 1.3 x 10-1 mbar, 133 C) 11.99g = 62 mmol = 78% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (m, 2H), (m, 3H), 4.04 (s_br, 1H), 3.80 (s_br, 1H), 3.24 (dd, J = 12.6, 2.6 Hz, 1H), 2.97 (dd, J = 12.6, 8.6Hz, 1H), 1.95 (d, J = 1.9 Hz, 1H), (m, 6H), 0.93 (t, J = 6.7 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 149.2, 129.7, 118.0, 113.6, 70.9, 50.8, 35.4, 28.4, 23.3, 14.4 ppm. MS (70 ev, EI); m/z (%): 193 (6, M + ), 118 (2), 106 (100), 93 (3), 77 (9). 3d: 5-benzyl-2-butyl--phenyl-1H-pyrrol-3-amine: Cat. II (3.0 ml, 0.03 mmol, 0.01 M in THF), 1-phenylamino-hexan-2-ol (3.86 g, 20.0 mmol), 2-amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 8:1 4:1 pentane : Et 2 O; Yield: 2.49 g = 8.2 mmol = 82% as deep red oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.51 (s_br, 1H), (m, 2H), (m, 3H), (m, 2H), (m, 3H), 5.79 (d, J = 2.9 Hz, 1H), 4.96 (s_br, 1H), 3.91 (s, 2H), (m, 2H), (m, 2H), 0.87 (t, J = 7.3 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 149.4, 140.5, 129.5, , , 128.1, 127.0, 126.8, 121.5, 117.5, 113.5, 105.7, 34.9, 32.4, 25.2, 23.0, 14.2 ppm. MS (70 ev, EI); m/z (%): 304 (1, M + ), 261 (66), 244 (13), 169 (100), 115 (15), 91 (15). elemental analysis (%) for C 21 H 24 2 calcd: C 82.85, H 7.95, 9.20; found: C 82.53, H 8.02, 9.15 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

37 1-(6-methylpyridin-2-ylamino)butan-2-ol: Cat. II (0.3 mmol, 215 mg), 6-methylpyridin-2- amine (10.8 g, mmol) butane-1,2-diol (18.4 ml, mmol), 60 ml THF, KO t Bu (12.4g, mmol), 96 h at 110 C. Purification by HV distillation (2.6x 10-2 mbar, 122 C); Yield: 16.0 g = 89.0 mmol = 89% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 7.29 (dd, J = 8.3,7.2 Hz, 1H), 6.43 (d, J = 7.2 Hz, 1H), 6.27 (d, J = 8.3 Hz, 1H), 4.98 (s_br, 1H), (m, 1H), (m, 1H), (m, 1H), 2.32 (s, 3H), (m, 2H), 0.94 (t, J = 7.6 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ =159.3, 156.5, 138.4, 112.4, 105.6, 74.3, 49.3, 28.7, 24.2, 10.5 ppm. 3e: -(5-benzyl-2-ethyl-1H-pyrrol-3-yl)-6-methylpyridin-2-amine: Cat. II (3.0 ml, 0.03 mmol, 0.01 M in THF), 1-(6-methyl-pyridin-2-ylamino)-butan-2-ol (3.60 g, 20.0 mmol), 2- amino-3-phenyl-propan-1-ol (1.51 g, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 2:1 1:2 pentane : Et 2 O; Yield: 2.53 g = 8.7 mmol = 87% as deep red oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.14 (s_br, 1H), (m, 6H), 6.46 (d, J = 7.0 Hz, 1H), 6.30 (s_br, 1H), 6.27 (d, J = 8.5 Hz, 1H), 5.83 (d, J = 2.9 Hz, 1H), 3.94 (s, 2H), 2.49 (q, J = 7.6 Hz, 2H), 2.34 (s, 3H), 1.11 (t, J = 7.6 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 16.1, 157.2, 140.5, 138.3, 129.1, 129.0, , 126.8, 119.3, 112.5, 105.9, 103.3, 34.8, 24.4, 18.8, 14.4 ppm. MS (70 ev, EI); m/z (%): 291 (42, M + ), 276 (50), 184 (100), 168 (35), 142 (30), 115 (32), 91 (44). elemental analysis (%) for C 19 H 21 3 calcd C 78.32, H 7.26, 14.42; found: C 78.08, H ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

38 Supplementary Table S14: Reaction of 1-phenylethanol with 1-amino-alcohol to 4-substituted pyrroles [mol% Cat. II] Product Yield [a] % [a] Isolated yield 4-ethyl-2-phenyl-1H-pyrrole: Cat. II (5.0 ml, 0.05 mmol, 0.01 M in THF), 1-phenylethanol (2.4 ml, 20.0 mmol) 1-aminobutan-2-ol (960 µl, 10.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 10:1 pentane : Et 2 O; Yield: 889 mg = 5.2 mmol = 52% as colorless solid. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.28 (s_br, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), (m, 1H), 2.53 (q, J = 7.5 Hz, 2H), 1.22 (t, J = 7.6 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 133.5, 132.1, 129.4, 128.6, 126.4, 124.0, 116.2, 106.5, 20.7, 15.7 ppm. MS (70 ev, EI); m/z (%): 171 (46), 156 (100), 128 (20), 115 (10), 78 (19). 2,5-diethylpyrazine: Cat. II (71 mg, 0.1 mmol), 2-aminobutan-1-ol (3.8 ml, 40.0 mmol), 10 ml THF, KO t Bu (2.5 g, 22.0 mmol), 24 h at 90 C. Purification by column chromatography 5:1 pentane : Et 2 O; Yield: 0.54 g = 3.9 mmol = 19% as yellow oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 8.33 (s, 2H), 2.77 (q, J = 7.6 Hz, 4H), 1.27 (t, J = 7.6 Hz, 6H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 156.2,143.3, 28.7, 13.9 ppm. MS (70 ev, EI); m/z (%): 136, (55, M + ), 135 (100), 121 (96), 108 (8), 94 (4), 80 (5), 67 (6). ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

39 2-(1-phenylethylideneamino)butan-1-ol: acetophenone (35.0 ml, mmol) (±)2- aminobutan-1-ol (33.0 ml, mmol), molecular sieve 3Ǻ (40 g), 200 ml THF, 48 h reflux. Purification by HV distillation (3.0 x 10-3, 52 C); Yield: 53.5 g = mmol = 93% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (m, 2H), (m, 3H), 4.09 (dd, J = 7.7, 6.9 Hz, 0.31 H), 3.76 (t, J = 7.3 Hz, 0.65H), 3.32 (t, J = 7.7 Hz, 0.69 H), (m, 0.35 H), 1.85 (s_br, 1H), (m, 5H), (m, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 146.2, 128.5, 127.6, 126.4, 125.9, 71.2, 60.4, 29.9, 27.2, 11.8 ppm. MS (70 ev, EI); m/z (%): 190 (1), 176 (100), 160 (75), 145 (8), 132 (7), 114 (50), 105 (63), 91 (33), 77 (32). 2-(1-phenylpentylideneamino)butan-1-ol: valerophenone (20.0 ml, mmol) (±)2- aminobutan-1-ol (19.0 ml, mmol), molecular sieve 3Ǻ (20 g), 200 ml THF, 48 h reflux. Purification by HV distillation (3.8 x 10-2, 110 C); Yield: 21.5 g = 92.2 mmol = 76% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (m, 2H), (m, 3H), (m, 0.28H), 3.76 (t, J = 7.4 Hz, 0.71H), (m, 1H), (m, 1H), 1.95 (s_br, 1H), (m, 2H), (m, 1H), (m, 1H), (m, 4H), (m, 3H), (m, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 145.8, 128.2, 127.5, 127.1, 126.5, 71.1, 61.0, 60.1, 42.3, 26.9, 23.5, 14.3, 11.7 ppm. MS (70 ev, EI); m/z (%): 233 (1, M + ), 232 (1), 202 (11), 176 (100), 156 (6), 120 (7), 105 (35), 91 (12), 77 (16). 2-(phenylamino)ethanol: cat. II (0.5 mmol, 359 mg), aniline (23.3 ml, mmol) ethane- 1,2-diol (50.0 ml, mmol), 200 ml THF, KO t Bu (31.0 g, mmol), 72 h at 110 C. Purification by HV distillation (2.3 x 10-1, 107 C); Yield: g = 80.0 mmol = 32% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (m, 2H), (m, 1H), (m, 2H), 4.08 (s_br, 1H), 3.77 ( t, J = 5.3 Hz, 2H), 3.25 (t, J = 5.3 Hz, 2H), 2.44 (s_br, 1H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 149.0, 129.7, 118.1, 113.6, 61.6, 46.6 ppm. MS (70 ev, EI); m/z (%): 137 (25, M + ), 106 (100), 77 (20). ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

40 tert-butyl-1-hydroxybutan-2-ylcarbamate: To 2-aminobutan-1-ol (18.9 ml, 200 mmol) in 500 ml water and 400 ml THF was added a 2 CO 3 (70.0 g, 660 mmol). After cooling to 0 C, di-tert-butyl-dicarbonate (45.0 g, 206 mmol) dissolved in 100 ml THF was added drop wise. The solution was allowed to warm to room temperature and stirred for further 4h. The solution was extracted 4 times with Et 2 O. The combined organic phases were dried over a 2 SO 4, filtered and the solvent was removed by rotary evaporation. Purification by HV distillation (8.8 x 10-2 mbar, 99 C); Yield: 36.5 g = 192 mmol = 96% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = 4.73 (s_br, 1H), (m, 1H), (m, 2H), 2.67 (s_br, 1H), (m, 2H), 1.42 (s, 9H), 0.93 (t, J = 7.6 Hz, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 157.1, 79.6, 65.6, 54.8, 28.7, 25.1, 10.9 ppm. (5-methylcyclohexa-1,3-diene-1,3,5-triyl)tribenzene: Cat. II (36 mg, 0.05 mmol), 1-phenyl-1- ethanol (2.4 ml, 20.0 mmol), 10 ml THF, KO t Bu (1.24 g, 11.0 mmol), 24 h at 90 C. Purification by column chromatography 100:1 pentane : Et 2 O 3:1 pentane : Et 2 O; Yield: = 527 mg = 1.6 mmol = 33% as colorless oil. 1 H MR (300 MHz, CD 2 Cl 2 ): δ = (m, 15H), 6.79 (q, J = 1.5 Hz,1H)), 6.27 (d, J = 1.5 Hz, 1H), 3.18 (dd, J = 16.7, 1.5 Hz, 1H), 2.89 (dd, J = 16.7, 1.8 Hz, 1H), 1.64 (s, 3H) ppm. 13 C MR (75 MHz, CD 2 Cl 2 ): δ = 149.3, 141.5, 141.2, 137.6, 136.5, 132.7, 129.1, 129.0, 128.8, 128.0, 127.0, 126.7, 126.6, 126.4, 125.8, 121.9, 41.9, 40.9, 27.5 ppm. MS (70 ev, EI); m/z (%): 322 (100, M + ), 307 (80), 291 (14), 265 (8), 231 (24), 215 (31), 202 (12), 165 (8), 115 (9), 105 (29), 91 (17), 77 (10). ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

41 Mechanistic Studies Synthesis of [(4-Ph)Tr(HP(iPr) 2 ) 2 IrH 3 ] Cat. II (1.0 mmol, 719 mg) was dissolved in 4 ml benzene-d 6 and stirred in a 60 bar H 2 atmosphere at 25 C for 2 days. An orange solution was obtained. Crystals suitable for X-Ray analysis were obtained from this solution. Due to the high reactivity of this compound MRanalyses was done directly from the reaction solution. 1 H MR (400 MHz, C 6 D 6 ): δ = (m, 2H), (m, 3H), 5.90 (s_br, 2H), (m, 4H), (m, 24H), (dt, J = 18.3, 5.1 Hz, 2H), (tt, J = 14.6, 5.1 Hz, 1H) ppm. 13 C MR (100 MHz, C 6 D 6 ): δ = (t, J = 9.5 Hz), 168.4, 137.1, 132.2, 129.1, 129.0, 69.3, 30.8 (t, J = 16.2 Hz), 28.8, 26.2, 23.9, 19.5 (t, J = 4.4 Hz), 18.8 ppm. 31 P MR (161 MHz, C 6 D 6, 298 K): δ = (dt, J = 13.0, 6.7 Hz) ppm. elemental analysis (%) for [C 21 H 35 Ir 5 P 2 ] x 0.4 C 6 D 6 calcd: C 43.35, H 6.65, 10.80; found: C 43.42, H 6.65, ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

42 Supplementary Figure S3: Formation of the catalyst resting state, an iridium trihydride complex. It can be formed quantitatively by reacting catalyst II with alcohols, H 2 or under catalytic conditions conversion [%] reaction time [h] Supplementary Figure S4. Time conversion plot for the reaction of 1-phenylethanol with 2-amino-butan-1-ol. reaction conditions: 1-phenylethanol (2.4 ml, 20.0 mmol), 2-amino-butan-1-ol (1.92 ml, 20.0 mmol), KO t Bu (2.48 g, 22.0 mmol), cat. II (57 mg, 0.08 mmol), 20 ml dioxane, ml dodecane as internal standard, 110 C 2-ethyl-5-phenyl-1H-pyrrole 1-phenylethanol acetophenone (5-methylcyclohexa-1,3-diene-1,3,5- triyl)tribenzene ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

43 conversion [%] reaction time [h] Supplementary Figure S5. Time conversion plot for the reaction of 1-phenylethanol with 2-amino-butan-1-ol. reaction conditions: 1-phenylethanol (4.8 ml, 40.0 mmol), 2-amino-butan-1-ol (1.92 ml, 20.0 mmol), KO t Bu (2.48 g, 22.0 mmol), cat. II (57 mg, 0.08 mmol), 20 ml dioxane, ml dodecane as internal standard, 110 C 2-ethyl-5-phenyl-1H-pyrrole 1-phenylethanol acetophenone (5-methylcyclohexa-1,3-diene-1,3,5- triyl)tribenzene Possible Reaction Pathways Supplementary Figure S6: Possible reaction pathways for the pyrrole synthesis ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

44 Reactions which confirm Pathway A Supplementary Figure S7: Dehydrogenation of 1-phenylethanol Without base 1-phenylethanol is converted into acetophenone and H 2 by catalyst II, but with base, 1-phenylethanol is converted to acetophenone and several additional aldol condensation products (Supplementary Figure S7). Due to this fact the system 1-phenyl-1- pentanol/valerophenone was used for further mechanistic investigations (Supplementary Figure S9). Supplementary Figure S8: Conversion of 2-(1-phenylethylideneamino)butan-1-ol to 2-ethyl-5-phenyl-1H-pyrrole Under catalytic conditions 2-(1-phenylethylideneamino)butan-1-ol is converted to 2-ethyl-5- phenyl-1h-pyrrole in excellent yield (Supplementary Figure S8). If catalyst or base is used exclusively only a very poor conversion of the imine is observed. This fact clearly points out that both catalyst and base in combination are involved in the cyclisation reaction. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

45 Supplementary Figure S9: Dehydrogenation of 1-phenyl-1-pentanol to valerophenone under catalytic conditions Dehydrogenation of 1-phenyl-1-pentanol is fast. Under standard reaction conditions the secondary alcohol is completely converted to the corresponding ketone within 24 h (Supplementary Figure S9). Supplementary Figure S10: Dehydrogenation and condensation reaction of 2-amino-1-butanol to 2,5- diethylpyrazine In contrast the dehydrogenation and condensation reaction of the amino alcohol to 2,5- diethylpyrazine is very slow under the given reaction conditions (90 C), which was already shown in our previous work. 38 (Supplementary Figure S10) ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

46 Supplementary Figure S11: Pathway A1: reaction of valerophenone with 2-amino-1-butanol under catalytic conditions (cat II, 0.5 mol%) Pathway A2: reaction of 2-(1-phenylpentylideneamino)butan-1-ol under catalytic conditions (cat II, 0.5 mol%) Regardless whether the reaction was started from ketone and amino alcohol (A1, Supplementary Figure S11), or from the preformed Schiff base (A2, Supplementary Figure S11), nearly identical yields were obtained. This indicates that the imine formation is very fast Reactions which contradict Pathway B Supplementary Figure S12: Under catalytic conditions no reaction of 1-phenylethanol with 2- (phenylamino)ethanol is observed ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

47 Supplementary Figure S13: Under catalytic conditions no reaction of 1-phenylethanol with tert-butyl-1- hydroxybutan-2-ylcarbamate o ß-alkylation between 1-phenylethanol and the -protected amino alcohol was observed, regardless which protecting group was chosen (Supplementary Figure S12 and Supplementary Figure S13). These experiments show that under the given reaction conditions the ß-alkylation is very unlikely to be the first reaction step (pathway B, Supplementary Figure S6) in the pyrrole syntheses. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

48 Crystal Structure of [(4-Ph)Tr(P( i Pr) 2 )(HP( i Pr) 2 )Ir(cod)]; (Catalyst II) Supplementary Figure S14: Crystal structure of catalyst II data_t257ofma1 _audit_creation_method SHELXL-97 _chemical_name_systematic ;? ; _chemical_name_common? _chemical_melting_point? _chemical_formula_moiety? _chemical_formula_sum 'C29 H46 Ir 5 P2' _chemical_formula_weight loop atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 'International Tables Vol C Tables and ' 'H' 'H' 'International Tables Vol C Tables and ' '' '' ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

49 'International Tables Vol C Tables and ' 'P' 'P' 'International Tables Vol C Tables and ' 'Ir' 'Ir' 'International Tables Vol C Tables and ' _symmetry_cell_setting _symmetry_space_group_name_h-m orthorhombic Fdd2 loop symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/4, y+1/4, z+1/4' 'x+1/4, -y+1/4, z+1/4' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' '-x+1/4, y+3/4, z+3/4' 'x+1/4, -y+3/4, z+3/4' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' '-x+3/4, y+1/4, z+3/4' 'x+3/4, -y+1/4, z+3/4' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' '-x+3/4, y+3/4, z+1/4' 'x+3/4, -y+3/4, z+1/4' _cell_length_a (11) _cell_length_b (2) _cell_length_c (12) _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume (14) _cell_formula_units_z 16 _cell_measurement_temperature 133(2) _cell_measurement_reflns_used _cell_measurement_2theta_min 3.56 _cell_measurement_2theta_max _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.19 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas? _exptl_crystal_density_diffrn _exptl_crystal_density_method 'not measured' _exptl_crystal_f_ _exptl_absorpt_coefficient_mu _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_t_min _exptl_absorpt_correction_t_max _exptl_absorpt_process_details? _exptl_special_details ;? ; _diffrn_ambient_temperature 133(2) _diffrn_radiation_wavelength ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

50 _diffrn_radiation_type _diffrn_radiation_source _diffrn_radiation_monochromator _diffrn_measurement_device_type _diffrn_measurement_method _diffrn_detector_area_resol_mean? _diffrn_standards_number? _diffrn_standards_interval_count? _diffrn_standards_interval_time? _diffrn_standards_decay_%? _diffrn_reflns_number _diffrn_reflns_av_r_equivalents _diffrn_reflns_av_sigmai/neti _diffrn_reflns_limit_h_min -23 _diffrn_reflns_limit_h_max 23 _diffrn_reflns_limit_k_min -49 _diffrn_reflns_limit_k_max 49 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.78 _diffrn_reflns_theta_max _reflns_number_total 5231 _reflns_number_gt 3973 _reflns_threshold_expression >2\s(I) MoK\a 'fine-focus sealed tube' graphite STOE-IPDSII Omega-Scan _computing_data_collection X-AREA-STOE _computing_cell_refinement X-AREA-STOE _computing_data_reduction X-RED32 _computing_structure_solution SIR-97 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics? _computing_publication_material? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(fo^2^)+(0.0846p)^2^ p] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, ' _refine_ls_abs_structure_flack 0.014(17) _refine_ls_number_reflns 5231 _refine_ls_number_parameters 318 _refine_ls_number_restraints 4 _refine_ls_r_factor_all _refine_ls_r_factor_gt ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

51 _refine_ls_wr_factor_ref _refine_ls_wr_factor_gt _refine_ls_goodness_of_fit_ref _refine_ls_restrained_s_all _refine_ls_shift/su_max _refine_ls_shift/su_mean loop atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_u_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ir1 Ir (3) (14) (4) (18) Uani 1 1 d... P1 P (2) (9) (2) (9) Uani 1 1 d... P2 P (18) (9) (4) (10) Uani 1 1 d (6) (3) (9) 0.050(3) Uani 1 1 d (6) (3) (8) 0.045(3) Uani 1 1 d (6) (4) (8) 0.062(4) Uani 1 1 d (6) (3) (8) 0.049(3) Uani 1 1 d... H1 H Uiso 1 1 calc R (7) (3) (10) 0.064(4) Uani 1 1 d... C1 C (9) (4) (11) 0.060(3) Uani 1 1 d... H1 H Uiso 1 1 calc R.. C2 C (9) (4) (12) 0.060(3) Uani 1 1 d... H2 H Uiso 1 1 calc R.. C3 C (9) (4) (12) 0.066(3) Uani 1 1 d... H3A H Uiso 1 1 calc R.. H3B H Uiso 1 1 calc R.. C4 C (11) (4) (13) 0.077(4) Uani 1 1 d D.. H4A H Uiso 1 1 calc R.. H4B H Uiso 1 1 calc R.. C5 C (18) (5) (17) 0.141(9) Uani 1 1 d D.. H5 H Uiso 1 1 calc R.. C6 C (15) (6) (18) 0.141(9) Uani 1 1 d D.. H6 H Uiso 1 1 calc R.. C7 C (10) (4) (13) 0.077(4) Uani 1 1 d D.. H7A H Uiso 1 1 calc R.. H7B H Uiso 1 1 calc R.. C8 C (9) (4) (11) 0.066(3) Uani 1 1 d... H8A H Uiso 1 1 calc R.. H8B H Uiso 1 1 calc R.. C9 C (7) (4) (10) 0.050(4) Uani 1 1 d... C10 C (8) (3) (9) 0.048(4) Uani 1 1 d... C11 C (8) (4) (11) 0.054(4) Uani 1 1 d... C12 C (8) (4) (11) 0.054(4) Uani 1 1 d... H12 H Uiso 1 1 calc R.. C13 C (8) (4) (11) 0.058(4) Uani 1 1 d... H13 H Uiso 1 1 calc R.. C14 C (9) (5) (14) 0.071(5) Uani 1 1 d... H14 H Uiso 1 1 calc R.. C15 C (8) (4) (11) 0.057(4) Uani 1 1 d... H15 H Uiso 1 1 calc R.. C16 C (8) (4) (10) 0.056(4) Uani 1 1 d... H16 H Uiso 1 1 calc R.. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

52 C17 C (7) (3) (9) 0.043(3) Uani 1 1 d... C18 C (10) (4) (14) 0.067(5) Uani 1 1 d... H18A H Uiso 1 1 calc R.. H18B H Uiso 1 1 calc R.. H18C H Uiso 1 1 calc R.. C19 C (9) (4) (12) 0.066(5) Uani 1 1 d... H19A H Uiso 1 1 calc R.. H19B H Uiso 1 1 calc R.. H19C H Uiso 1 1 calc R.. C20 C (9) (5) (13) 0.069(5) Uani 1 1 d... H20A H Uiso 1 1 calc R.. H20B H Uiso 1 1 calc R.. H20C H Uiso 1 1 calc R.. C21 C (12) (6) (14) 0.093(7) Uani 1 1 d... H21A H Uiso 1 1 calc R.. H21B H Uiso 1 1 calc R.. H21C H Uiso 1 1 calc R.. C22 C (9) (4) (12) 0.066(4) Uani 1 1 d... H22A H Uiso 1 1 calc R.. H22B H Uiso 1 1 calc R.. H22C H Uiso 1 1 calc R.. C23 C (10) (5) (16) 0.090(7) Uani 1 1 d... H23A H Uiso 1 1 calc R.. H23B H Uiso 1 1 calc R.. H23C H Uiso 1 1 calc R.. C24 C (11) (5) (14) 0.081(6) Uani 1 1 d... H24A H Uiso 1 1 calc R.. H24B H Uiso 1 1 calc R.. H24C H Uiso 1 1 calc R.. C25 C (11) (6) (14) 0.087(6) Uani 1 1 d... H25A H Uiso 1 1 calc R.. H25B H Uiso 1 1 calc R.. H25C H Uiso 1 1 calc R.. C26 C (9) (5) (12) 0.065(5) Uani 1 1 d... H26 H Uiso 1 1 calc R.. C27 C (8) (4) (9) 0.047(3) Uani 1 1 d... H27 H Uiso 1 1 calc R.. C28 C (9) (5) (12) 0.071(5) Uani 1 1 d... H28 H Uiso 1 1 calc R.. C29 C (8) (4) (9) 0.049(4) Uani 1 1 d... H29 H Uiso 1 1 calc R.. loop atom_site_aniso_label _atom_site_aniso_u_11 _atom_site_aniso_u_22 _atom_site_aniso_u_33 _atom_site_aniso_u_23 _atom_site_aniso_u_13 _atom_site_aniso_u_12 Ir (3) (3) (3) (3) (3) (3) P (2) 0.056(2) 0.042(2) (16) (16) (17) P (2) 0.063(2) 0.056(2) 0.014(3) 0.008(3) (17) (7) 0.046(7) 0.065(8) 0.005(6) 0.000(6) 0.009(6) (7) 0.039(7) 0.054(7) (5) 0.001(6) (5) (7) 0.088(10) 0.050(7) (7) (6) 0.025(7) (7) 0.057(8) 0.046(7) (6) 0.002(6) 0.003(6) (9) 0.071(10) 0.061(9) 0.006(7) 0.005(7) 0.006(7) C (8) 0.042(6) 0.068(8) (5) (6) 0.010(6) C (8) 0.042(6) 0.068(8) (5) (6) 0.010(6) C (8) 0.069(8) 0.061(7) (6) 0.010(6) (6) C (9) 0.070(8) 0.075(9) (7) 0.016(8) (7) C5 0.22(3) 0.080(12) 0.124(16) 0.006(12) 0.010(18) (14) ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

53 C6 0.22(3) 0.080(12) 0.124(16) 0.006(12) 0.010(18) (14) C (9) 0.070(8) 0.075(9) (7) 0.016(8) (7) C (8) 0.069(8) 0.061(7) (6) 0.010(6) (6) C (8) 0.069(10) 0.048(8) (8) 0.001(6) 0.000(8) C (9) 0.048(9) 0.041(7) 0.005(6) (7) 0.000(7) C (9) 0.068(11) 0.050(8) 0.005(8) (7) 0.000(8) C (9) 0.066(11) 0.052(9) (8) (7) 0.005(8) C (9) 0.068(10) 0.059(11) 0.010(8) (7) 0.014(8) C (10) 0.074(13) 0.087(13) 0.015(10) (10) (9) C (9) 0.072(12) 0.047(8) 0.000(8) 0.004(7) 0.007(9) C (9) 0.052(8) 0.059(11) (7) (8) (8) C (8) 0.043(8) 0.036(7) (6) (6) 0.012(7) C (11) 0.074(12) 0.072(12) 0.011(10) (9) (9) C (12) 0.064(11) 0.064(10) 0.013(8) (9) 0.003(9) C (10) 0.077(12) 0.077(11) (10) (9) 0.000(9) C (14) 0.13(2) 0.073(13) 0.016(13) (11) (14) C (10) 0.066(11) 0.074(11) 0.007(9) 0.006(9) 0.002(9) C (11) 0.106(16) 0.109(16) 0.059(14) (11) (11) C (16) 0.056(11) 0.086(13) 0.008(10) 0.038(12) 0.006(11) C (13) 0.113(17) 0.072(12) (12) (10) 0.020(13) C (10) 0.079(12) 0.071(11) (9) 0.006(8) 0.007(9) C (8) 0.053(9) 0.040(8) 0.005(7) 0.005(6) (7) C (11) 0.087(13) 0.060(11) 0.011(9) 0.018(9) 0.012(10) C (8) 0.058(9) 0.046(8) 0.006(7) 0.001(7) (7) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. ; loop geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ir (16).? Ir1 C (17).? Ir1 C (18).? Ir1 P (4).? Ir1 P (4).? P (13).? P1 C (16).? P1 C (15).? P (15).? P2 C (18).? P2 C (19).? 1 C (19).? 1 C9 1.37(2).? 2 C (18).? 2 C (19).? 3 C9 1.41(2).? 3 C (19).? 4 C (18).? 5 C9 1.36(2).? C1 C2 1.39(2).? C1 C8 1.52(2).? ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

54 C2 C3 1.50(2).? C3 C4 1.53(2).? C4 C (17).? C5 C (18).? C6 C (17).? C7 C8 1.57(2).? C10 C (2).? C11 C (2).? C11 C (2).? C12 C (2).? C13 C (2).? C14 C (3).? C15 C (2).? C18 C (2).? C19 C (2).? C20 C (2).? C21 C (3).? C22 C (2).? C23 C (3).? C24 C (3).? C25 C (3).? loop geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag 3 Ir1 C (5)..? 3 Ir1 C (5)..? C1 Ir1 C2 38.1(6)..? 3 Ir1 P2 78.7(4)..? C1 Ir1 P2 91.1(5)..? C2 Ir1 P2 98.6(5)..? 3 Ir1 P1 81.4(4)..? C1 Ir1 P (5)..? C2 Ir1 P1 99.4(5)..? P2 Ir1 P (14)..? 4 P1 C (6)..? 4 P1 C (6)..? C29 P1 C (7)..? 4 P1 Ir1 98.6(5)..? C29 P1 Ir (5)..? C27 P1 Ir (5)..? 5 P2 C (8)..? 5 P2 C (8)..? C26 P2 C (8)..? 5 P2 Ir (5)..? C26 P2 Ir (6)..? C28 P2 Ir (6)..? C10 1 C (12)..? C17 2 C (13)..? C9 3 C (14)..? C9 3 Ir (10)..? C17 3 Ir (11)..? C17 4 P (11)..? C9 5 P (12)..? C2 C1 C (15)..? C2 C1 Ir1 71.1(11)..? C8 C1 Ir (11)..? C1 C2 C (15)..? ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

55 C1 C2 Ir1 70.7(10)..? C3 C2 Ir (13)..? C2 C3 C (16)..? C5 C4 C (17)..? C6 C5 C4 123(3)..? C5 C6 C7 130(2)..? C6 C7 C (17)..? C1 C8 C (13)..? 5 C (14)..? 5 C (14)..? 1 C (13)..? 2 C (13)..? 2 C10 C (14)..? 1 C10 C (13)..? C12 C11 C (15)..? C12 C11 C (15)..? C16 C11 C (15)..? C11 C12 C (15)..? C14 C13 C (18)..? C13 C14 C (18)..? C16 C15 C (15)..? C15 C16 C (15)..? 4 C (13)..? 4 C (14)..? 2 C (13)..? C25 C26 C (17)..? C25 C26 P (12)..? C24 C26 P (13)..? C18 C27 C (14)..? C18 C27 P (11)..? C19 C27 P (10)..? C23 C28 C (17)..? C23 C28 P (15)..? C21 C28 P (13)..? C20 C29 C (14)..? C20 C29 P (11)..? C22 C29 P (11)..? _diffrn_measured_fraction_theta_max _diffrn_reflns_theta_full _diffrn_measured_fraction_theta_full _refine_diff_density_max _refine_diff_density_min _refine_diff_density_rms ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

56 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

57 Alert level B occurs because the compound crystallises in very thin plates. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

58 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

59 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

60 Crystal Structure of [(4-Ph)Tr(HP(iPr) 2 )IrH 3 ] (catalyst resting state) Supplementary Figure S15. Crystal Structure of [(4-Ph)Tr(HP(iPr) 2 )IrH 3 ] data_t356hpma _audit_creation_method SHELXL-97 _chemical_name_systematic ;? ; _chemical_name_common? _chemical_melting_point? _chemical_formula_moiety? _chemical_formula_sum 'C33 H47 Ir 5 P2' _chemical_formula_weight loop atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

61 'International Tables Vol C Tables and ' 'H' 'H' 'International Tables Vol C Tables and ' '' '' 'International Tables Vol C Tables and ' 'P' 'P' 'International Tables Vol C Tables and ' 'Ir' 'Ir' 'International Tables Vol C Tables and ' _symmetry_cell_setting trigonal _symmetry_space_group_name_h-m P3(2) loop symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z+2/3' '-x+y, -x, z+1/3' _cell_length_a (4) _cell_length_b (4) _cell_length_c (3) _cell_angle_alpha _cell_angle_beta _cell_angle_gamma _cell_volume (2) _cell_formula_units_z 9 _cell_measurement_temperature 133(2) _cell_measurement_reflns_used _cell_measurement_2theta_min 2.31 _cell_measurement_2theta_max _exptl_crystal_description prism _exptl_crystal_colour orange _exptl_crystal_size_max 0.44 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas? _exptl_crystal_density_diffrn _exptl_crystal_density_method 'not measured' _exptl_crystal_f_ _exptl_absorpt_coefficient_mu _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_t_min _exptl_absorpt_correction_t_max _exptl_absorpt_process_details? _exptl_special_details ;? ; ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

62 _diffrn_ambient_temperature 133(2) _diffrn_radiation_wavelength _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type STOE-IPDSII _diffrn_measurement_method Omega-Scan _diffrn_detector_area_resol_mean? _diffrn_standards_number? _diffrn_standards_interval_count? _diffrn_standards_interval_time? _diffrn_standards_decay_%? _diffrn_reflns_number _diffrn_reflns_av_r_equivalents _diffrn_reflns_av_sigmai/neti _diffrn_reflns_limit_h_min -27 _diffrn_reflns_limit_h_max 27 _diffrn_reflns_limit_k_min -27 _diffrn_reflns_limit_k_max 27 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 1.16 _diffrn_reflns_theta_max _reflns_number_total _reflns_number_gt _reflns_threshold_expression >2\s(I) _computing_data_collection X-AREA-STOE _computing_cell_refinement X-AREA-STOE _computing_data_reduction X-AREA-STOE _computing_structure_solution SIR-97 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics? _computing_publication_material? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type fullcycle _refine_ls_weighting_scheme calc _refine_ls_weighting_details ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

63 'calc w=1/[\s^2^(fo^2^)+(0.0414p)^2^ p] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, ' _refine_ls_abs_structure_flack (5) _refine_ls_number_reflns _refine_ls_number_parameters 881 _refine_ls_number_restraints 1 _refine_ls_r_factor_all _refine_ls_r_factor_gt _refine_ls_wr_factor_ref _refine_ls_wr_factor_gt _refine_ls_goodness_of_fit_ref _refine_ls_restrained_s_all _refine_ls_shift/su_max _refine_ls_shift/su_mean loop atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_u_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C (5) (5) (6) 0.029(2) Uani 1 1 d... C2 C (5) (5) (5) 0.033(2) Uani 1 1 d... C3 C (5) (5) (6) 0.035(2) Uani 1 1 d... C4 C (5) (4) (6) 0.036(2) Uani 1 1 d... H4 H Uiso 1 1 calc R.. C5 C (5) (5) (7) 0.051(3) Uani 1 1 d... H5 H Uiso 1 1 calc R.. C6 C (6) (5) (7) 0.054(3) Uani 1 1 d... H6 H Uiso 1 1 calc R.. C7 C (6) (5) (6) 0.046(3) Uani 1 1 d... H7 H Uiso 1 1 calc R.. C8 C (5) (5) (6) 0.043(3) Uani 1 1 d... H8 H Uiso 1 1 calc R.. C9 C (4) (4) (5) (18) Uani 1 1 d... C10 C (6) (6) (8) 0.057(3) Uani 1 1 d... ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

64 H10A H Uiso 1 1 calc R.. H10B H Uiso 1 1 calc R.. H10C H Uiso 1 1 calc R.. C11 C (5) (5) (7) 0.052(3) Uani 1 1 d... H11A H Uiso 1 1 calc R.. H11B H Uiso 1 1 calc R.. H11C H Uiso 1 1 calc R.. C12 C (6) (5) (7) 0.046(3) Uani 1 1 d... H12 H Uiso 1 1 calc R.. C13 C (7) (6) (7) 0.059(4) Uani 1 1 d... H13A H Uiso 1 1 calc R.. H13B H Uiso 1 1 calc R.. H13C H Uiso 1 1 calc R.. C14 C (6) (5) (7) 0.051(3) Uani 1 1 d... H14A H Uiso 1 1 calc R.. H14B H Uiso 1 1 calc R.. H14C H Uiso 1 1 calc R.. C15 C (7) (7) (8) 0.064(4) Uani 1 1 d... H15A H Uiso 1 1 calc R.. H15B H Uiso 1 1 calc R.. H15C H Uiso 1 1 calc R.. C16 C (8) (6) (8) 0.077(4) Uani 1 1 d... H16A H Uiso 1 1 calc R.. H16B H Uiso 1 1 calc R.. H16C H Uiso 1 1 calc R.. C17 C (5) (6) (8) 0.055(3) Uani 1 1 d... H17A H Uiso 1 1 calc R.. H17B H Uiso 1 1 calc R.. H17C H Uiso 1 1 calc R.. C18 C (7) (6) (7) 0.059(4) Uani 1 1 d... H18A H Uiso 1 1 calc R.. H18B H Uiso 1 1 calc R.. H18C H Uiso 1 1 calc R.. C19 C (6) (6) (7) 0.051(3) Uani 1 1 d... H19A H Uiso 1 1 calc R.. H19B H Uiso 1 1 calc R.. H19C H Uiso 1 1 calc R.. C20 C (8) (7) (10) 0.078(5) Uani 1 1 d... H20A H Uiso 1 1 calc R.. H20B H Uiso 1 1 calc R.. H20C H Uiso 1 1 calc R.. C21 C (5) (6) (7) 0.056(3) Uani 1 1 d... H21A H Uiso 1 1 calc R.. H21B H Uiso 1 1 calc R.. H21C H Uiso 1 1 calc R.. C22 C (5) (5) (7) 0.047(3) Uani 1 1 d... H22A H Uiso 1 1 calc R.. H22B H Uiso 1 1 calc R.. H22C H Uiso 1 1 calc R.. C23 C (5) (4) (6) 0.031(2) Uani 1 1 d... C24 C (4) (5) (5) 0.031(2) Uani 1 1 d... ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

65 C25 C (4) (4) (5) 0.028(2) Uani 1 1 d... C26 C (6) (6) (7) 0.059(3) Uani 1 1 d... H26A H Uiso 1 1 calc R.. H26B H Uiso 1 1 calc R.. H26C H Uiso 1 1 calc R.. C27 C (5) (5) (6) 0.032(2) Uani 1 1 d... C28 C (5) (5) (7) 0.047(3) Uani 1 1 d... H28A H Uiso 1 1 calc R.. H28B H Uiso 1 1 calc R.. H28C H Uiso 1 1 calc R.. C29 C (6) (6) (7) 0.051(3) Uani 1 1 d... H29A H Uiso 1 1 calc R.. H29B H Uiso 1 1 calc R.. H29C H Uiso 1 1 calc R.. C30 C (7) (8) (9) 0.060(4) Uani 1 1 d... H30A H Uiso 1 1 calc R.. H30B H Uiso 1 1 calc R.. H30C H Uiso 1 1 calc R.. C31 C (7) (7) (9) 0.061(4) Uani 1 1 d... H31A H Uiso 1 1 calc R.. H31B H Uiso 1 1 calc R.. H31C H Uiso 1 1 calc R.. C32 C (6) (6) (7) 0.048(3) Uani 1 1 d... H32A H Uiso 1 1 calc R.. H32B H Uiso 1 1 calc R.. H32C H Uiso 1 1 calc R.. C33 C (5) (5) (7) 0.049(3) Uani 1 1 d... H33A H Uiso 1 1 calc R.. H33B H Uiso 1 1 calc R.. H33C H Uiso 1 1 calc R.. C34 C (6) (5) (7) 0.051(3) Uani 1 1 d... H34A H Uiso 1 1 calc R.. H34B H Uiso 1 1 calc R.. H34C H Uiso 1 1 calc R.. C35 C (5) (6) (8) 0.065(3) Uani 1 1 d... H35A H Uiso 1 1 calc R.. H35B H Uiso 1 1 calc R.. H35C H Uiso 1 1 calc R.. C36 C (8) (7) (10) 0.089(5) Uani 1 1 d... H36A H Uiso 1 1 calc R.. H36B H Uiso 1 1 calc R.. H36C H Uiso 1 1 calc R.. C37 C (5) (5) (5) 0.030(2) Uani 1 1 d... C38 C (4) (5) (5) (19) Uani 1 1 d... C39 C (6) (6) (8) 0.060(3) Uani 1 1 d... H39A H Uiso 1 1 calc R.. H39B H Uiso 1 1 calc R.. H39C H Uiso 1 1 calc R.. C40 C (6) (7) (7) 0.052(3) Uani 1 1 d... H40A H Uiso 1 1 calc R.. H40B H Uiso 1 1 calc R.. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

66 H40C H Uiso 1 1 calc R.. C41 C (5) (5) (7) 0.042(2) Uani 1 1 d... H41 H Uiso 1 1 calc R.. C42 C (5) (5) (7) 0.033(3) Uani 1 1 d... H42 H Uiso 1 1 calc R.. C43 C (6) (5) (6) 0.045(3) Uani 1 1 d... H43 H Uiso 1 1 calc R.. C44 C (6) (5) (7) 0.036(2) Uani 1 1 d... H44 H Uiso 1 1 calc R.. C45 C (6) (6) (7) 0.043(3) Uani 1 1 d... H45 H Uiso 1 1 calc R.. C46 C (5) (5) (6) 0.041(2) Uani 1 1 d... H46 H Uiso 1 1 calc R.. C47 C (6) (7) (7) 0.062(3) Uani 1 1 d... H47 H Uiso 1 1 calc R.. C48 C (6) (6) (7) 0.057(3) Uani 1 1 d... H48 H Uiso 1 1 calc R.. C49 C (5) (6) (6) 0.050(3) Uani 1 1 d... H49 H Uiso 1 1 calc R.. C50 C (5) (5) (5) 0.036(2) Uani 1 1 d... C51 C (5) (5) (6) 0.045(2) Uani 1 1 d... H51 H Uiso 1 1 calc R.. C52 C (6) (6) (7) 0.062(3) Uani 1 1 d... H52 H Uiso 1 1 calc R.. C53 C (5) (4) (6) 0.042(2) Uani 1 1 d... H53 H Uiso 1 1 calc R.. C54 C (5) (5) (5) 0.032(2) Uani 1 1 d... C55 C (5) (5) (5) 0.037(2) Uani 1 1 d... H55 H Uiso 1 1 calc R.. C56 C (5) (5) (6) 0.037(2) Uani 1 1 d... H56 H Uiso 1 1 calc R.. C57 C (6) (5) (6) 0.052(3) Uani 1 1 d... H57 H Uiso 1 1 calc R.. C58 C (5) (5) (6) 0.042(2) Uani 1 1 d... H58 H Uiso 1 1 calc R.. C59 C (5) (5) (6) 0.043(2) Uani 1 1 d... H59 H Uiso 1 1 calc R.. C60 C (5) (6) (8) 0.041(3) Uani 1 1 d... H60 H Uiso 1 1 calc R.. C61 C (5) (6) (6) 0.047(3) Uani 1 1 d... H61 H Uiso 1 1 calc R.. C62 C (6) (6) (6) 0.049(3) Uani 1 1 d... H62 H Uiso 1 1 calc R.. C63 C (6) (7) (7) 0.047(3) Uani 1 1 d... H63 H Uiso 1 1 calc R.. C64 C (4) (3) (5) 0.059(3) Uiso 1 1 d G.. H64 H Uiso 1 1 calc R.. C65 C (3) (3) (5) 0.073(3) Uiso 1 1 d G.. H65 H Uiso 1 1 calc R.. C66 C (3) (3) (5) 0.058(3) Uiso 1 1 d G.. H66 H Uiso 1 1 calc R.. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

67 C67 C (3) (3) (5) 0.057(3) Uiso 1 1 d G.. H67 H Uiso 1 1 calc R.. C68 C (3) (3) (5) 0.065(3) Uiso 1 1 d G.. H68 H Uiso 1 1 calc R.. C69 C (3) (4) (5) 0.061(3) Uiso 1 1 d G.. H69 H Uiso 1 1 calc R.. C70 C (4) (3) (5) 0.090(4) Uiso 1 1 d G.. H70 H Uiso 1 1 calc R.. C71 C (4) (4) (5) 0.060(3) Uiso 1 1 d G.. H71 H Uiso 1 1 calc R.. C72 C (3) (4) (5) 0.074(3) Uiso 1 1 d G.. H72 H Uiso 1 1 calc R.. C73 C (4) (3) (6) 0.106(5) Uiso 1 1 d G.. H73 H Uiso 1 1 calc R.. C74 C (5) (4) (6) 0.093(4) Uiso 1 1 d G.. H74 H Uiso 1 1 calc R.. C75 C (3) (5) (6) 0.081(4) Uiso 1 1 d G.. H75 H Uiso 1 1 calc R.. C76 C (3) (4) (6) 0.078(3) Uiso 1 1 d G.. H76 H Uiso 1 1 calc R.. C77 C (4) (4) (6) 0.074(3) Uiso 1 1 d G.. H77 H Uiso 1 1 calc R.. C78 C (4) (3) (5) 0.075(3) Uiso 1 1 d G.. H78 H Uiso 1 1 calc R.. C79 C (3) (4) (5) 0.080(4) Uiso 1 1 d G.. H79 H Uiso 1 1 calc R.. C80 C (4) (4) (6) 0.086(4) Uiso 1 1 d G.. H80 H Uiso 1 1 calc R.. C81 C (4) (3) (5) 0.064(3) Uiso 1 1 d G.. H81 H Uiso 1 1 calc R.. C82 C (4) (3) (5) 0.068(3) Uiso 1 1 d G.. H82 H Uiso 1 1 calc R.. C83 C (3) (4) (5) 0.077(4) Uiso 1 1 d G.. H83 H Uiso 1 1 calc R.. C84 C (3) (3) (6) 0.077(4) Uiso 1 1 d G.. H84 H Uiso 1 1 calc R.. C85 C (4) (3) (6) 0.081(4) Uiso 1 1 d G.. H85 H Uiso 1 1 calc R.. C86 C (4) (4) (6) 0.082(4) Uiso 1 1 d G.. H86 H Uiso 1 1 calc R.. C87 C (3) (4) (6) 0.084(4) Uiso 1 1 d G.. H87 H Uiso 1 1 calc R.. C88 C (4) (4) (6) 0.103(5) Uiso 1 1 d G.. H88 H Uiso 1 1 calc R.. C89 C (5) (4) (6) 0.079(4) Uiso 1 1 d G.. H89 H Uiso 1 1 calc R.. C90 C (4) (5) (6) 0.091(4) Uiso 1 1 d G.. H90 H Uiso 1 1 calc R.. C91 C (4) (4) (7) 0.115(5) Uiso 1 1 d G.. H91 H Uiso 1 1 calc R.. C92 C (5) (4) (6) 0.097(5) Uiso 1 1 d G.. ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

68 H92 H Uiso 1 1 calc R.. C93 C (5) (5) (6) 0.090(4) Uiso 1 1 d G.. H93 H Uiso 1 1 calc R.. C94 C (6) (3) (7) 0.107(5) Uiso 1 1 d G.. H94 H Uiso 1 1 calc R.. C95 C (4) (4) (6) 0.092(4) Uiso 1 1 d G.. H95 H Uiso 1 1 calc R.. C96 C (5) (4) (6) 0.093(4) Uiso 1 1 d G.. H96 H Uiso 1 1 calc R.. C97 C (5) (3) (6) 0.076(3) Uiso 1 1 d G.. H97 H Uiso 1 1 calc R.. C98 C (4) (5) (6) 0.112(5) Uiso 1 1 d G.. H98 H Uiso 1 1 calc R.. C99 C (6) (5) (7) 0.117(6) Uiso 1 1 d G.. H99 H Uiso 1 1 calc R (4) (4) (4) (16) Uani 1 1 d (4) (4) (5) (17) Uani 1 1 d (3) (3) (5) (16) Uani 1 1 d (4) (4) (4) (17) Uani 1 1 d... H4A H Uiso 1 1 calc (4) (4) (5) (18) Uani 1 1 d... H5A H Uiso 1 1 calc (4) (4) (5) (17) Uani 1 1 d (4) (4) (5) (17) Uani 1 1 d (4) (4) (5) (16) Uani 1 1 d (4) (4) (5) (18) Uani 1 1 d... H9 H Uiso 1 1 calc (4) (4) (5) (18) Uani 1 1 d... H10 H Uiso 1 1 calc (4) (4) (4) (19) Uani 1 1 d (4) (4) (5) (17) Uani 1 1 d (4) (4) (4) (16) Uani 1 1 d (4) (4) (5) (18) Uani 1 1 d... H14 H Uiso 1 1 calc (4) (4) (5) (17) Uani 1 1 d... H15 H Uiso 1 1 calc... P1 P (13) (12) (14) (5) Uani 1 1 d... P2 P (15) (14) (15) (6) Uani 1 1 d... P3 P (15) (14) (16) (6) Uani 1 1 d... P4 P (13) (14) (14) (5) Uani 1 1 d... P5 P (12) (12) (14) (5) Uani 1 1 d... P6 P (13) (12) (17) (6) Uani 1 1 d... Ir1 Ir (4) (17) (15) (10) Uani 1 1 d... Ir2 Ir (3) (3) (18) (10) Uani 1 1 d... Ir3 Ir (17) (17) (3) (7) Uani 1 1 d... loop atom_site_aniso_label _atom_site_aniso_u_11 _atom_site_aniso_u_22 _atom_site_aniso_u_33 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

69 _atom_site_aniso_u_23 _atom_site_aniso_u_13 _atom_site_aniso_u_12 C (5) 0.040(5) 0.024(5) (4) (4) 0.030(4) C (5) 0.038(5) 0.023(5) (4) 0.011(4) 0.020(4) C (5) 0.035(4) 0.029(5) (4) 0.005(4) 0.012(4) C (5) 0.030(4) 0.039(5) (4) 0.008(4) 0.021(4) C (6) 0.040(5) 0.059(7) 0.005(5) 0.006(5) 0.021(5) C (7) 0.028(5) 0.065(7) 0.014(5) 0.022(6) 0.022(5) C (6) 0.039(6) 0.032(6) (4) 0.007(5) 0.017(5) C (6) 0.034(6) 0.038(6) 0.004(4) 0.010(5) 0.020(5) C (4) 0.025(4) 0.022(5) 0.000(4) (4) 0.010(4) C (6) 0.060(7) 0.063(8) (6) 0.000(5) 0.026(5) C (6) 0.042(6) 0.050(6) (5) (5) 0.014(5) C (7) 0.036(6) 0.044(6) (5) (5) 0.019(5) C (9) 0.055(7) 0.038(6) 0.018(5) 0.019(6) 0.039(7) C (6) 0.045(6) 0.050(7) (5) 0.002(5) 0.024(5) C (9) 0.082(9) 0.052(7) (7) (7) 0.061(8) C (13) 0.072(9) 0.072(9) (7) (8) 0.076(10) C (7) 0.059(7) 0.056(7) (6) 0.001(5) 0.031(5) C (10) 0.040(7) 0.041(7) (5) 0.002(7) 0.031(6) C (7) 0.050(6) 0.042(6) (5) (5) 0.030(5) C (13) 0.079(10) 0.077(11) (8) (8) 0.061(9) C (6) 0.061(7) 0.066(8) 0.025(6) 0.018(5) 0.036(5) C (5) 0.060(6) 0.042(6) 0.003(5) 0.000(4) 0.019(5) C (5) 0.029(4) 0.024(5) (4) (4) 0.012(4) C (5) 0.043(5) 0.020(5) (4) (4) 0.021(4) C (4) 0.031(4) 0.020(5) (4) (4) 0.012(4) C (8) 0.042(6) 0.048(7) 0.005(5) 0.020(6) 0.017(6) C (5) 0.032(5) 0.035(6) 0.000(4) (4) 0.021(4) C (6) 0.050(6) 0.050(6) (5) (5) 0.026(5) C (6) 0.057(7) 0.054(7) (6) (5) 0.028(6) C (8) 0.089(9) 0.054(8) (7) (6) 0.070(8) C (8) 0.073(9) 0.067(8) (7) (7) 0.055(8) C (6) 0.053(6) 0.036(6) (5) (5) 0.027(5) C (5) 0.048(5) 0.045(6) 0.004(5) 0.009(5) 0.014(4) C (6) 0.045(6) 0.044(6) 0.004(5) 0.001(5) 0.016(5) C (5) 0.079(8) 0.083(9) 0.006(7) 0.011(5) 0.035(6) C (11) 0.065(8) 0.113(13) 0.042(8) 0.033(10) 0.060(8) C (5) 0.041(5) 0.021(4) (4) (4) 0.023(4) C (4) 0.036(5) 0.016(4) (4) (4) 0.013(4) C (7) 0.046(6) 0.071(8) 0.017(5) 0.006(6) 0.024(5) C (7) 0.076(8) 0.039(6) (6) (5) 0.052(6) C (6) 0.041(6) 0.040(6) (4) (5) 0.024(5) C (5) 0.038(5) 0.028(7) 0.006(4) 0.009(4) 0.028(5) C (7) 0.039(5) 0.033(6) 0.001(4) (5) 0.032(5) C (6) 0.021(5) 0.035(6) (4) (5) 0.011(5) C (6) 0.048(6) 0.043(7) (5) 0.003(5) 0.029(5) C (5) 0.052(6) 0.038(6) 0.010(5) 0.009(5) 0.033(5) C (8) 0.090(10) 0.057(8) (7) (6) 0.056(7) C (7) 0.073(8) 0.056(7) (6) 0.002(6) 0.054(7) ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

70 C (6) 0.067(7) 0.044(6) (5) (5) 0.040(6) C (6) 0.047(5) 0.023(4) (4) (4) 0.033(4) C (6) 0.049(6) 0.047(6) (5) (5) 0.032(5) C (9) 0.065(7) 0.069(8) (6) (7) 0.060(7) C (6) 0.033(5) 0.034(5) (4) (5) 0.023(4) C (5) 0.043(5) 0.022(5) (4) (4) 0.030(4) C (6) 0.041(5) 0.021(5) (4) (4) 0.023(5) C (6) 0.042(5) 0.032(6) 0.000(4) 0.007(4) 0.030(5) C (7) 0.053(6) 0.042(6) (5) 0.004(5) 0.049(6) C (6) 0.041(5) 0.048(6) 0.008(4) 0.016(5) 0.039(5) C (6) 0.054(6) 0.040(5) 0.007(4) 0.003(4) 0.040(5) C (6) 0.041(6) 0.061(8) (5) 0.000(5) 0.024(5) C (5) 0.060(7) 0.047(6) 0.008(5) 0.001(5) 0.026(5) C (7) 0.052(6) 0.031(6) (5) 0.007(5) 0.037(6) C (7) 0.068(9) 0.040(6) 0.009(6) 0.006(5) 0.048(7) (4) 0.052(4) 0.014(4) (4) 0.004(3) 0.026(4) (4) 0.025(4) 0.027(4) (3) (3) 0.006(3) (3) 0.023(3) 0.031(4) 0.001(3) 0.000(3) 0.010(3) (4) 0.034(4) 0.013(4) (3) (3) 0.021(3) (4) 0.034(4) 0.023(4) (3) (3) 0.016(3) (4) 0.034(4) 0.033(4) (4) 0.005(4) 0.015(3) (4) 0.037(4) 0.028(4) (3) (3) 0.024(3) (4) 0.031(4) 0.029(4) (3) (3) 0.018(3) (4) 0.040(5) 0.029(4) 0.002(3) 0.004(3) 0.027(4) (4) 0.038(4) 0.026(4) 0.002(3) 0.003(4) 0.020(4) (4) 0.057(5) 0.014(4) (4) (3) 0.015(4) (4) 0.025(3) 0.031(5) (3) (3) 0.021(3) (4) 0.030(4) 0.022(4) (3) (3) 0.025(3) (4) 0.044(5) 0.021(4) 0.007(3) 0.004(3) 0.023(3) (4) 0.037(4) 0.022(4) 0.004(3) 0.007(3) 0.023(4) P (13) (11) (12) (10) (10) (10) P (15) (13) (12) (11) (12) (13) P (15) (13) (13) (11) (11) (13) P (13) (13) (12) (11) (10) (11) P (13) (12) (12) (10) (10) (10) P (12) (14) (14) (11) (10) (11) Ir (2) (17) (2) (15) (19) (17) Ir (2) (2) (2) (18) (17) (2) Ir (17) (2) (17) (17) (19) (14) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. ; loop_ ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

71 _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C (13).? C (13).? C (12).? C (13).? C (12).? C2 C (13).? C3 C (14).? C3 C (15).? C4 C (13).? C5 C (17).? C6 C (17).? C7 C (14).? C (11).? C (12).? C (12).? C10 C (15).? C11 C (14).? C12 C (17).? C12 C (16).? C12 P (13).? C15 C (17).? C16 C (15).? C17 C (16).? C18 C (15).? C19 C (16).? C20 C (18).? C21 C (13).? C22 C (15).? C (12).? C (13).? C (13).? C (12).? C (12).? C24 C (13).? C (12).? C (13).? C (12).? C26 C (18).? C (14).? C (13).? C (11).? C28 C (16).? C29 C (15).? C30 C (15).? C31 C (15).? C32 C (15).? ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

72 C33 C (14).? C34 C (16).? C35 C (14).? C36 C (15).? C (13).? C (12).? C37 C (13).? C (12).? C (12).? C (13).? C39 C (14).? C40 C (15).? C41 P (11).? C42 P (12).? C43 P (11).? C44 P (12).? C45 P (12).? C46 P (10).? C47 C (18).? C47 C (18).? C48 C (14).? C49 C (15).? C50 C (14).? C51 C (14).? C53 P (10).? C54 C (14).? C54 C (14).? C55 C (13).? C56 C (15).? C57 C (14).? C58 C (12).? C60 P (13).? C61 P (11).? C62 P (12).? C63 P (13).? C64 C ? C64 C ? C65 C ? C66 C ? C67 C ? C68 C ? C70 C ? C70 C ? C71 C ? C72 C ? C73 C ? C74 C ? C76 C ? C76 C ? C77 C ? C78 C ? ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

73 C79 C ? C80 C ? C82 C ? C82 C ? C83 C ? C84 C ? C85 C ? C86 C ? C88 C ? C88 C ? C89 C ? C90 C ? C91 C ? C92 C ? C94 C ? C94 C ? C95 C ? C96 C ? C97 C ? C98 C ? 1 Ir (8).? 4 P (8).? 5 P (8).? 6 Ir (7).? 9 P (8).? 10 P (8).? 11 Ir (8).? 14 P (8).? 15 P (8).? P1 Ir (3).? P2 Ir (3).? P3 Ir (3).? P4 Ir (3).? P5 Ir (2).? P6 Ir (3).? loop geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag 5 C (8)..? 5 C (9)..? 1 C (8)..? 2 C (9)..? 2 C2 C (9)..? 3 C2 C (9)..? C4 C3 C (9)..? ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

74 C4 C3 C (9)..? C8 C3 C (9)..? C3 C4 C (10)..? C6 C5 C (10)..? C5 C6 C (9)..? C6 C7 C (11)..? C3 C8 C (10)..? 2 C (8)..? 2 C (8)..? 4 C (7)..? C14 C12 C (10)..? C14 C12 P (9)..? C13 C12 P (8)..? 13 C (9)..? 13 C (8)..? 11 C (8)..? 12 C (9)..? 12 C24 C (8)..? 13 C24 C (8)..? 12 C (9)..? 12 C (9)..? 11 C (8)..? 10 C (8)..? 10 C (9)..? 6 C (9)..? 7 C (8)..? 7 C37 C (8)..? 8 C37 C (8)..? 7 C (9)..? 7 C (8)..? 6 C (8)..? C11 C41 C (9)..? C11 C41 P (8)..? C10 C41 P (7)..? C40 C42 C (10)..? C40 C42 P (8)..? C32 C42 P (8)..? C15 C43 C (10)..? C15 C43 P (8)..? C16 C43 P (9)..? C17 C44 C (11)..? C17 C44 P (8)..? C18 C44 P (8)..? C20 C45 C (11)..? C20 C45 P (9)..? C19 C45 P (8)..? C22 C46 C (9)..? C22 C46 P (7)..? C21 C46 P (7)..? C48 C47 C (11)..? C47 C48 C (12)..? ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

75 C50 C49 C (11)..? C49 C50 C (9)..? C49 C50 C (10)..? C51 C50 C (9)..? C50 C51 C (10)..? C47 C52 C (12)..? C33 C53 C (8)..? C33 C53 P (7)..? C39 C53 P (7)..? C59 C54 C (9)..? C59 C54 C (8)..? C55 C54 C (9)..? C54 C55 C (9)..? C57 C56 C (9)..? C58 C57 C (8)..? C57 C58 C (9)..? C54 C59 C (9)..? C31 C60 C (10)..? C31 C60 P (9)..? C29 C60 P (8)..? C34 C61 C (10)..? C34 C61 P (7)..? C35 C61 P (8)..? C36 C62 C (11)..? C36 C62 P (9)..? C26 C62 P (8)..? C28 C63 C (11)..? C28 C63 P (8)..? C30 C63 P (9)..? C65 C64 C ? C64 C65 C ? C67 C66 C ? C66 C67 C ? C69 C68 C ? C68 C69 C ? C71 C70 C ? C70 C71 C ? C73 C72 C ? C72 C73 C ? C75 C74 C ? C74 C75 C ? C77 C76 C ? C78 C77 C ? C77 C78 C ? C80 C79 C ? C81 C80 C ? C80 C81 C ? C83 C82 C ? C82 C83 C ? C83 C84 C ? C84 C85 C ? ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

76 C87 C86 C ? C86 C87 C ? C89 C88 C ? C88 C89 C ? C91 C90 C ? C90 C91 C ? C93 C92 C ? C92 C93 C ? C95 C94 C ? C96 C95 C ? C97 C96 C ? C96 C97 C ? C97 C98 C ? C98 C99 C ? C1 1 C (8)..? C1 1 Ir (6)..? C9 1 Ir (6)..? C2 2 C (8)..? C2 3 C (8)..? C9 4 P (6)..? C1 5 P (7)..? C27 6 C (8)..? C27 6 Ir (6)..? C38 6 Ir (7)..? C38 7 C (8)..? C27 8 C (8)..? C38 9 P (7)..? C27 10 P (7)..? C23 11 C (8)..? C23 11 Ir (7)..? C25 11 Ir (6)..? C24 12 C (8)..? C23 13 C (8)..? C25 14 P (7)..? C23 15 P (7)..? 4 P1 C (4)..? 4 P1 C (4)..? C41 P1 C (5)..? 4 P1 Ir (3)..? C41 P1 Ir (4)..? C44 P1 Ir (4)..? 5 P2 C (4)..? 5 P2 C (5)..? C43 P2 C (6)..? 5 P2 Ir (3)..? C43 P2 Ir (4)..? C12 P2 Ir (4)..? 9 P3 C (4)..? 9 P3 C (5)..? C63 P3 C (5)..? 9 P3 Ir (3)..? ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

77 C63 P3 Ir (4)..? C62 P3 Ir (4)..? 10 P4 C (5)..? 10 P4 C (5)..? C60 P4 C (6)..? 10 P4 Ir2 99.6(3)..? C60 P4 Ir (4)..? C61 P4 Ir (4)..? 14 P5 C (4)..? 14 P5 C (4)..? C53 P5 C (5)..? 14 P5 Ir (3)..? C53 P5 Ir (3)..? C42 P5 Ir (4)..? 15 P6 C (4)..? 15 P6 C (5)..? C46 P6 C (5)..? 15 P6 Ir (3)..? C46 P6 Ir (4)..? C45 P6 Ir (4)..? 1 Ir1 P1 82.4(2)..? 1 Ir1 P2 81.3(2)..? P1 Ir1 P (10)..? 6 Ir2 P3 82.4(2)..? 6 Ir2 P4 81.2(2)..? P3 Ir2 P (9)..? 11 Ir3 P5 82.3(2)..? 11 Ir3 P6 81.2(2)..? P5 Ir3 P (8)..? _diffrn_measured_fraction_theta_max _diffrn_reflns_theta_full _diffrn_measured_fraction_theta_full _refine_diff_density_max _refine_diff_density_min _refine_diff_density_rms ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

78 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

79 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.

80 ATURE CHEMISTRY Macmillan Publishers Limited. All rights reserved.