David L. Davies,*, 1 Charles E. Ellul, 1 Stuart A. Macgregor,*, 2 Claire L. McMullin 2 and Kuldip Singh. 1. Table of contents. General information

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1 Experimental Supporting Information for Experimental and DFT Studies Explain Solvent Control of C-H Activation and Product Selectivity in the Rh(III)-Catalyzed Formation of eutral and Cationic Heterocycles David L. Davies,*, 1 Charles E. Ellul, 1 Stuart A. Macgregor,*, 2 Claire L. McMullin 2 and Kuldip Singh. 1 1 Department of Chemistry, University of Leicester, Leicester, LE1 7RH, UK 2 Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK Table of contents General information Synthesis of 3a Synthesis of 4a[Cl] General procedure for catalytic C, coupling reactions Synthesis of 7a Synthesis of 7b X-ray Crystallography S2 S2 S3 S3 S9 S9 S10 1 H and 13 C MR spectra S20 References S32

2 General information Unless stated otherwise all reactions were carried out under an inert atmosphere of nitrogen, work up was carried out in air. Electrospray (ESI) mass spectra were recorded using a micromassquattra LCmass spectrometer with acetonitrile as the matrix. MR spectra were recorded on a Bruker DRX400 spectrometer operating at 400 ( 1 H) and 100 MHz ( 13 C) or a Bruker DRX500 spectrometer at 500 ( 1 H) and 125 MHz ( 13 C) at 298K; chemical shifts (ppm) are referred to the residual protic solvent peaks and coupling constants are expressed in Hertz (Hz). Assignments of 1 H MR and 13 C MR signals were made where possible, using OESY, HSQC, HMBC and APT experiments. All starting materials were obtained from Sigma Aldrich or Alfa Aesar and used without further purification. [RhCl 2 Cp * ] 2, 1 [Rh(MeC) 3 Cp * ][ ] 2, 2 2, 3 were prepared using literature procedures. Synthesis of 3a A Schlenk tube with a magnetic stirrer bar was charged with 2 (30 mg, mmol), the red solid was then dissolved in chloroform (5 ml) to which 4-octyne (40 mg, 0.36 mmol) was added and the solution was allowed to stir at room temperature for 5 days. After which, the solvent was removed in vacuo, and the product was extracted into hexane (10 ml). The product was isolated by removal of solvent as a crude mixture of 3a and Cp* Rh Cl a H MR (400 MHz, CDCl 3 ): δ 8.55 (d, 1 H, J = 2.37 Hz, H 1 ), 7.70 (d, 1 H, J = 2.63 Hz, H 3 ), 7.58 (dd, 1 H, J = 7.68, 1.21 Hz, H 5 ), 7.38 (td, 1 H, J = 7.68, 1.21 Hz, H 6 ), 7.16 (td, 1 H, J = 7.52, 1.42 Hz, H 7 ), 7.07 (dd, 1 H, J = 3.95, 1.42 Hz, H 8 ), 6.44 (t, 1 H, J = 2.54 Hz, H 2 ), 2.84 (td, 1 H, J = 12.50, 4.44 Hz, H 12 ), (m, 1 H, H 12 ), (m, 2 H, H 12 ), (m, 4 H, H 13 ) 0.86 (t, 3 H, J = 7.13 Hz, H 14 ), 0.57 (t, 3 H, J = 7.50 Hz, H 14 ). 13 C{ 1 H} MR (100 MHz, CDCl 3 ): δ (d, J CRh = Hz, C 11 ), (C 1 ), (C 4 ), (C 9 ), (C 10 ), (C 3 ), (C 5 ), (C 6 ) (C 8 ), S2

3 (C 7 ), (C 2 ), 95.7 (C 5 Me 5 ), 39.7 (C 12 ), 37.6 (C 12 ), 23.4 (C 13 ), 22.7 (C 13 ), 14.2 (C 14 ), 13.4 (C 14 ), 9.1 (C 5 Me 5 ); HRMS [ESI] for C 27 H 36 2 Rh 1 [M-Cl]: Calcd: ; Found: Synthesis of 4a[Cl] A Schlenk tube with a magnetic stirrer bar was charged with 2 (50 mg mmol), the red solid was then dissolved in methanol (5 ml) to which 4-octyne (13.3 mg, 0.12 mmol) was added. The solution was allowed to stir at room temperature for 3 hours. After which the solvent was removed in vacuo and the product was isolated as a white solid by recrystalisation from dichloromethane/hexane. Yield: 22 mg (80 %) Cl a[Cl] 1 H MR (500 MHz, CDCl 3 ): δ (brs, 1 H, H 3 ), 9.43 (brs, 1 H, H 1 ), 9.21 (d, 1 H, J = 7.43 Hz, H 5 ), (m, 2 H, H 6/7/8 ), 7.68 (t, 1 H, J = 7.65 Hz, H 6/7 ), 7.48 (brs, 1 H, H 2 ), (m, 2 H, H 12 ), (m, 2H, H 12 ), 1.81 (sextet, 2 H, J = 7.65 Hz, H 13 ), 1.70 (sextet. 2 H, J = 7.65 Hz, H 13 ), 1.19 (t, 3 H, J = 7.43 Hz, H 14 ), 1.14 (4, 3H, J = 7.43 Hz, H 14 ). 13 C{ 1 H} MR (125 MHz, CDCl 3 ): δ (C 10/11 ), (C 6/7/8 ), (C 3 ), (C 6/7 ), (C 4/9 ), (C 1 ), (C 6/7/8 ), (C 10/11 ), (C 4/9 ), (C 5 ), (C 2 ), 30.3 (C 12 ), 29.4 (C 12 ), 23.2 (C 13 ), 20.1 (C 13 ), 14.4 (C 14 ), 14.0 (C 14 ); HRMS (ESI) for C 17 H 21 2 [M + ]: Calcd: ; Found: General procedure for catalytic C, coupling reactions Ethanol (10 ml), substrate (0.5 mmol) and alkyne (0.6 mmol), were placed into a Schlenk tube with a magnetic stirrer bar, followed by the addition of the rhodium catalyst ( mmol, 5 mol % {Rh}), K (0.6 mmol) and Cu(OAc) 2 H 2 O (1.25 mmol). The suspension was then stirred at 83 C in an oil bath. After cooling to room temperature the product was extracted into dichloromethane (2 x 10 ml) S3

4 and washed with water (20 ml) containing ethylene diamine (1 ml). The organic fraction was collected and dried over MgSO 4. The filtrate was concentrated and the product was isolated by column chromatography using alumina eluted with ethyl acetate/methanol (100:0 to 50:50 ethyl acetate:methanol) a[PF6] White sold, 145 mg (73%). 1 H MR (400 MHz, CD 2 Cl 2 ): δ 9.15 (d, 1 H, J = 3.18 Hz, H 3 ), 8.55 (d, 1 H, J = 2.98 Hz, H 1 ), 8.19 (dd, 1 H, J = 4.38, 0.99 Hz, H 5 ), 7.98 (dd, 1 H, J = 7.41, 0.99 Hz, H 8 ), (m, 2 H, H 6/7 ), 7.46 (t, 1 H, J = 3.18 Hz, H 2 ), (m, 2 H, H 12 ), (m, 2 H, H 12 ), 1.79 (sextet, 2 H, J = 7.57 Hz, H 13 ), 1.74 (sextet, 2 H, J = 7.57 Hz, H 13 ), 1.17 (t, 3 H, J = 7.46 Hz, H 14 ), 1.13 (t, 3 H, J = 7.46 Hz, H 14 ). 13 C{ 1 H} MR (100 MHz, CD 2 Cl 2 ): δ (C 10/11 ), (C 6 ), (C 7 ), (C 4/9 ), (C 1 ), (C 3 ), (C 8 ), (C 10/11 ), (C 4/9 ), (C 5 ), (C 2 ), 30.5 (C 12 ), 29.7 (C 12 ), 25.6 (C 13 ), 20.0 (C 13 ), 14.4 (C 14 ), 14.0 (C 14 ); HRMS (ESI) for C 17 H 21 2 [M + ]: Calcd: ; Found: aa[] Yellow solid, 157 mg (62%). 1 H MR (500 MHz, CDCl 3 ): δ 8.89 (d, 1 H, J = 3.63 Hz, H 1 ), 8.09 (dd, 1 H, J = 8.38, 0.83 Hz, H 6/8 ), 7.99 (t, 1 H, J = 8.03 Hz, H 7 ), 7.84 (dd, 1 H, J = 7.79, 0.74 Hz, H 6/8 ), 7.54 (d, 1 H, J = 7.54 Hz, H 2 ), , (m, 2 H, H 12 ), (m, 2 H, H 12 ), (m, 2 H, H 12 ), (m, 2 H, H 12 ), 1.84 (sextet, 2 H, J = 7.57 Hz, H 13 ), (m, 6 H, H 13 ), 1.19, (t, 3 H, J = 7.30 Hz, H 14 ), 1.17 (t, 3 H, J = 7.30 Hz, H 14 ), 1.16 (t, 3 H, J = 7.30 Hz, H 14 ), 1.13 (t, 3 H, J = 7.30 Hz, S4

5 H 14 ). 13 C{ 1 H} MR (125 MHz, CDCl 3 ): (C 5/9 ), (C 3 ), (C 10/11 ), (C 7 ), (C 10/11 ), (C 4 ), (C 1 ), (C 10/11 ), (C 5/9 ), (C 6/8 ), (C 10/11 ), (C 6/8 ), (C 2 ), 31.4 (C 12 ), 30.6 (C 12 ), 29.8 (C 12 ), 29.6 (C 12 ), 23.5 (C 13 ), 22.5 (C 13 ), 21.5 (C 13 ), 20.3 (C 13 ), 14.6 (C 14 ), 14.4 (C 14 ), 14.4 (C 14 ), 14.0 (C 14 ); HRMS (ESI) for C 25 H 33 2 [M + ]: Calcd: ; Found: ab[] Yellow solid, 186 mg (65%). 1 H MR (400 MHz, CDCl 3 ): δ 8.83 (d, 1 H, J = 3.47 Hz, H 1 ), 7.84 (overlapped d/t, 2 H, H 6/7 ), 7.65 (dd, 1 H, J = 3.84, 1.49 Hz, H 8 ), (m, 2 H, ), (m, 3 H, ), (m, 6 H,, H 2 ), (m, 2 H, H 12 ), (m, 2 H, H 12 ), 1.85 (sextet, 2H, J = 7.94 Hz, H 13 ), 1.77 (sextet, 2 H, J = 7.94 Hz, H 13 ), 1.18 (overlapped t, 6 H, J = 7.38 Hz, H 14 ). 13 C{ 1 H} MR (100 MHz, CDCl 3 ): δ (C Ar ), (C Ar ), (C Ar ), (C Ar ), (C Ar ), (C Ar-H ), (C Ar-H ), (C Ar ), (C Ar-H ), (C Ar-H ), (C 6 ), (C Ar ), (C Ar-H ), (C Ar-H ), (C 1 ), (C Ar ), (C 8 ), (C Ar ), (C Ar ), (C 7 ), (C 2 ), 29.8 (C 12 ), 29.7 (C 12 ), 21.5 (C 13 ), 20.2 (C 13 ), 14.4 (C 14 ), 14.0 (C 14 ); HRMS (ESI) for C 31 H 29 2 [M + ]: Calcd: ; Found: S5

6 ba[] 8 White solid, 141 mg (49%). 1 H MR (400 MHz, CDCl 3 ): δ 8.06 (d, 1 H, J = 3.46 Hz, H 1 ), 8.03 (br d, 1 H, J = 8.46 Hz, H 6 ), 7.79 (t, 1 H, J = 8.32 Hz, H 7 ), (m, 12 H,, H 2/8 ), (m, 2 H, H 12 ), (m, 2 H, H 12 ), (m, 4H, H 13 ), 1.17 (t, 3 H, J = 7.30 Hz, H 14 ), 1.11 (t, 3H, J = 7.30 Hz, H 14 ). 13 C{ 1 H} MR (100 MHz, CDCl 3 ): δ (C 10/11 ), (C Ar ), (C Ar ), (C Ar ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C 10/11 ), (C 7 ), (C Ar ), (C Ar ), (C Ar ), (C 1 ), (C Ar ), (C Ar ), (C Ar-H ), (C 8 ), (C 2 ), 31.4 (C 12 ), 30.6 (C 12 ), 23.4 (C 13 ), 22.4 (C 13 ), 14.6 (C 14 ), 14.3 (C 14 ); HRMS [ESI] C 31 H 29 2 [M + ]: Calcd: ; Found: bb[] 8 White solid, 100 mg (31%). 1 H MR (400 MHz, CDCl 3 ): δ 8.00 (d, 1 H, J = 3.39 Hz, H 1 ), 7.66 (d, 1 H, J = 4.42 Hz, H 6/8 ), 7.65 (br s, 1 H, H 6/8 ) (m, 21 H, /H 7 ), 7.00 (d, 1 H, J = 3.39 Hz, H 2 ). 13 C{ 1 H} MR (100 MHz, CDCl 3 ): δ (C Ar ), (C 3 ), (C Ar ), (C Ar ), (C 11 ), (C Ar ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C 6/8 ) (C Ar ), (C Ar ), (C 1 ), (C Ar ), (C Ar ), (C 6/8 ), (C Ar ), (C Ar ), (C 2 ); HRMS [ESI] C 37 H 25 2 [M+]: Calcd: ; Found: S6

7 a[] White solid, 147 mg (72%). 1 H MR (500 MHz, MeC-d 3 ): δ 8.62 (brs, 1 H, H 1/4 ), 8.60 (d, 1 H, J = 3.07 Hz, H 1/4 ), 8.24 (d, 1 H, J = 8.34 Hz, H 7 ), 7.87 (ddd, 1 H, J = 8.03, 6.85, 0.95 Hz, H 2/3 ), 7.68 (d, 1 H, J = 8.26 Hz, H 10 ), 7.50 (td, 1 H, J = 7.10, 1.27 Hz, H 2/3 ), 7.44 (ddd, 1 H, J = 8.49, 6.80, 0.95 Hz, H 9 ), 7.32 (ddd, 1 H, J = 8.78, 6.73, 0.95 Hz, H 8 ), (m, 2 H, H 14 ), (m, 2 H, H 14 ), 1.19 (sextet, 2 H, J = 7.60 Hz, H 15 ), 1.11 (sextet, 2 H, J = 7.60 Hz, H 15 ), 0.59 (t, 3 H, J = 7.32 Hz, H 16 ), 0.56 (t, 3 H, J = 7.32 Hz, H 16 ). 13 C{ 1 H} MR (125 MHz, MeC-d 3 ): δ (C Ar ), (C 2/3 ), (C Ar ), (C 1/4 ), (C 9 ), (C Ar ), (C Ar ), (C 8 ), (C 7 ), (C 10 ), (C 2/3 ), (C Ar ), (C 1/4 ), 32.0 (C 14 ), 31.6 (C 14 ), 24.3 (C 15 ), 20.8 (C 15 ), 14.6 (C 16 ), 14.2 (C 16 ); HRMS (ESI) for C 19 H 22 1 [M + ]: Calcd: ; Found: b[] White solid, 100 mg (42%). 1 H MR (500 MHz, MeC-d 3 ): δ 9.44 (d, 1 H, J = 8.26 Hz, H 4 ), 9.10 (d, 1 H, J = 8.37 Hz, H 7 ), 8.77 (d, 1 H, J = 6.87 Hz, H 1 ), 8.60 (ddd, 1 H, J = 9.05, 7.66, 1.19 Hz, H 3 ), 8.09 (ddd, 1 H, J = 8.71, 7.12, 1.44 Hz, H 8 ), 8.01 (ddd, 1 H, J = 8.50, 6.91, 1.10 Hz, H 9 ), 7.94 (td, 1 H, J = 7.13, 1.43 Hz, H 2 ), 7.60 (d, J = 8.55 Hz, H 10 ), (m, 5 H, ), (m, 3 H, ), (m, 2 H, ). 13 C{ 1 H} MR (100.6 MHz, MeC-d 3 ): δ (C Ar ), (C 3 ), (C Ar ), (C 1 ), (C Ar ), (C Ar ), (C 9 ), (C Ar ), (C Ar ), (C Ar-H ), (C 8 ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C 10 ), (C 7 ), (C Ar ), (C 2 ), (C 4 ); HRMS (ESI) for C 25 H 18 1 [M + ]: Calcd: ; Found: S7

8 a[] White solid, 120 mg (67%). 1 H MR (500 MHz, CDCl 3 ): δ 9.11 (d, 1 H, J = 7.44 Hz, H 1 ), 8.35 (d, 1 H, J = 7.93 Hz, H 4 ), 8.24 (d, 1 H, J = 8.43 Hz, H 6 ), 8.18 (t, 1 H, J = 7.93 Hz, H 3 ), (m, 2 H, H 2/7 ), (m, 2 H, H 10 ), (m, 2 H, H 10 ), (m, 4 H, H 11 ), 1.83 (t, 3 H, J = 7.36 Hz, H 12 ), 1.06 (t, 3 H, J = 7.36 Hz, H 12 ). 13 C{ 1 H} MR (125 MHz, CDCl 3 ): δ (C 8/9 ), (C 5 ), (C 2/7 ), (C 8/9 ), (C 3 ), (C 1 ), (C 4 ), (C 6 ), (C 2/7 ), 35.4 (C 10 ), 30.2 (C 10 ), 23.7 (C 11 ), 19.7 (C 11 ), 13.9 (C 12 ), 13.9 (C 12 ); HRMS (ESI) for C 15 H 20 1 [M + ]: Calcd: ; Found: b[] White solid, 97 mg (45%). 1 H MR (500 MHz, MeC-d 3 ): δ 8.66 (d, 1 H, J = 7.17 Hz, H 1 ), 8.45 (d, 2 H, J = 8.94 Hz, H 4/6 ), 8.22 (d, 1 H, J = 8.88 Hz, H 7 ), 8.18, (t, 1 H, J = 7.78 Hz, H 3 ), 7.75 (dt, 1 H, J = 7.17, 1.08 Hz, H 2 ), (m, 3 H, ), (m, 2 H, ), (m, 3 H, ), (m, 2 H, ). 13 C{ 1 H} MR (125 MHz, MeC-d 3 ): δ (C Ar ), (C Ar ), (C Ar ), (C 7 ), (C 3 ), (C Ar ), (C 1 ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar ), (C Ar- H ), (C Ar-H ), (C 4/6 ), (C 4/6 ), (C 2 ); HRMS (ESI) for C 21 H 16 1 [M + ]: Calcd: ; Found: S8

9 Synthesis of 7a A Schlenk tube with a magnetic stirrer bar was charged with 6a (41 mg, 0.16 mmol), aoac (9 mg, 0.16 mmol), [RhCl 2 Cp * ] 2 (50 mg, 0.08 mmol) and methanol (10 ml). The solution was heated to 60 C and stirred for 16 h. After which, the solvent was removed in vacuo, and the product was isolated by column chromatography using alumina eluted with ethyl acetate/methanol (100:0 to 50:50 ethyl acetate:methanol). The product was isolated as a red solid. Yield 47 mg (56 %). Cp* 1 Rh a Cl 1 H MR (400 MHz, CDCl 3 ): δ 8.01 (d, 1H, J = 2.49 Hz, H 1 ), 7.86 (dd, 1H, J = 7.09, 0.73 Hz, H 6 ), 7.48 (dd 1H, J = 8.03, 0.83 Hz, H 8 ), 7.42 (t, 1H, J = 7.51 Hz, H 7 ), 6.54 (d, 1H, J = 2.49 Hz, H 2 ), (m, 2H, H 12 ), (m, 2H, H 12 ), 1.73 (s, 15H, Cp*), (m, 4H, H 13 ), 1.11 (t, 3H, J = 7.36 Hz, H 14 ), 1.06 (t, 3H, J = 7.36, H 14 ). 13 C{ 1 H} MR (100 MHz, CDCl 3 ): δ (d, J CRh = Hz, C 9 ), (C 1 ), (C 3 ), (C 4/5 ), (C 10/11 ) (C 6 ), (C 7 ), (C 10/11 ), (C 4/5 ), (C 8 ), 98.0 (C 2 ), 95.4 (d, J CRh = 6.38 Hz, C 5 Me 5 ), 31.7 (C 12 ), 30.2 (C 12 ), 23.9 (C 13 ), 23.2 (C 13 ), 14.7 (C 14 ), 14.6 (C 14 ), 9.4 (C 5 Me 5 ); HRMS [ESI] C 27 H 34 2 Rh 1 [M-Cl]: Calcd: ; Found: Synthesis of 7b The reaction was carried and worked up using a similar method as 7a. In this case, 6b (51 mg, 0.16 mmol), aoac (9 mg, 0.16 mmol), [RhCl 2 Cp * ] 2 and methanol (10 ml) was used. The product was isolated as a red solid. Yield 66 mg (70%). S9

10 Cp* 1 Rh b 8 7 Cl 1 H MR (400 MHz, CDCl 3 ): δ 8.07 (d, 1H, J = 2.39 Hz, H 1 ), 7.94 (br d, 1H, J = 6.91 Hz, H 6 ), 7.35 (br t, 1H, J = 7.55 Hz, H 7 ), (m, 10H, ), 7.11 (dd, 1H, J = 4.14, 0.53 Hz, H 8 ), 6.44 (d, 1H, 2.50 Hz, H 2 ), 1.78 (s, 15H, Cp*). 13 C{ 1 H} MR (100 MHz, CDCl 3 ): δ (d, J CRh = Hz, C 9 ), (C 1 ), (C Ar ), (C Ar ), (C Ar ), (C Ar ), (C Ar ), (C 6 ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C Ar-H ), (C 10/11 ), (C Ar-H ), (C 10/11 ), (C 8 ), (C 2 ), 95.7 (d, J CRh = 7.62 Hz, C 5 Me 5 ), 9.57 (C 5 Me 5 ); HRMS [ESI] C 33 H 39 2 Rh 1 [M-Cl]: Calcd: ; Found: X-ray Crystallography Data were collected on a Bruker Apex 2000 CCD diffractometer using graphite monochromated Mo-Kα radiation, λ = Å. The data were corrected for Lorentz and polarisation effects and empirical absorption corrections were applied. The structure was solved by direct methods and with structure refinement on F² employed SHELXTL version Hydrogen atoms were included in calculated positions (C-H = Å) riding on the bonded atom with isotropic displacement parameters set to 1.5Ueq (C) for methyl hydrogen atoms and 1.2Ueq (C) for all other H atoms. All non-hydrogen atoms were refined with anisotropic displacement parameters without positional restraints. Figures were drawn using the program ORTEP. 5 S10

11 Table 1. Crystal data and structure refinement for 4a. Identification code Empirical formula C17 H21 F6 2 P Formula weight Temperature 150(2) K Wavelength Å Crystal system Monoclinic Space group Cc Unit cell dimensions a = (6) Å α= 90. b = (6) Å β= (7). c = 7.964(3) Å γ = 90. Volume (11) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 824 Crystal size 0.44 x 0.13 x 0.05 mm 3 Theta range for data collection 1.96 to Index ranges -18<=h<=18, -18<=k<=18, -9<=l<=9 Reflections collected 6589 Independent reflections 3250 [R(int) = ] Completeness to theta = % Absorption correction Empirical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3250 / 2 / 237 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.04(13) Largest diff. peak and hole and e.å -3 S11

12 Table 1. Crystal data and structure refinement for 5aa. Identification code Empirical formula C25 H33 F6 2 P Formula weight Temperature 150(2) K Wavelength Å Crystal system Monoclinic Space group C2/c Unit cell dimensions a = (3) Å α= 90. b = (5) Å β= (4). c = 8.917(2) Å γ = 90. Volume (9) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1064 Crystal size 0.31 x 0.14 x 0.07 mm 3 Theta range for data collection 1.89 to Index ranges -14<=h<=14, -25<=k<=25, -10<=l<=10 Reflections collected 8568 Independent reflections 2097 [R(int) = ] Completeness to theta = % Absorption correction Empirical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2097 / 0 / 159 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S12

13 Table 1. Crystal data and structure refinement for 5ba. Identification code Empirical formula C31 H33 Cl 2 O2 Formula weight Temperature 150(2) K Wavelength Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = (15) Å α= (4). b = (2) Å β= (4). c = (3) Å γ = (4). Volume (4) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 532 Crystal size 0.43 x 0.37 x 0.11 mm 3 Theta range for data collection 1.44 to Index ranges -9<=h<=9, -13<=k<=14, -16<=l<=17 Reflections collected 7384 Independent reflections 4455 [R(int) = ] Completeness to theta = % Absorption correction Empirical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4455 / 4 / 327 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S13

14 Table 1. Crystal data and structure refinement for 5bb. Identification code Empirical formula C38 H26 Cl3 F6 2 P Formula weight Temperature 150(2) K Wavelength Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = (17) Å α= (3). b = (2) Å β= (3). c = (2) Å γ = (3). Volume (5) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 776 Crystal size 0.24 x 0.21 x 0.11 mm 3 Theta range for data collection 1.63 to Index ranges -12<=h<=12, -15<=k<=15, -16<=l<=16 Reflections collected Independent reflections 6675 [R(int) = ] Completeness to theta = % Absorption correction Empirical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6675 / 541 / 460 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S14

15 Table 1. Crystal data and structure refinement for 7a. Identification code Empirical formula C27 H34 Cl 2 Rh Formula weight Temperature 150(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = (4) Å α= 90. b = 7.906(2) Å β= (6). c = (6) Å γ = 90. Volume (12) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1088 Crystal size 0.19 x 0.15 x 0.07 mm 3 Theta range for data collection 1.66 to Index ranges -16<=h<=16, -9<=k<=9, -29<=l<=28 Reflections collected Independent reflections 4851 [R(int) = ] Completeness to theta = % Absorption correction Empirical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4851 / 0 / 287 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S15

16 Table 1. Crystal data and structure refinement for 7b. Identification code Empirical formula C34 H31 Cl4 2 Rh Formula weight Temperature 150(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = (3) Å α= 90. b = (5) Å β= (4). c = (3) Å γ = 90. Volume (12) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1448 Crystal size 0.24 x 0.20 x 0.13 mm 3 Theta range for data collection 1.88 to Index ranges -14<=h<=14, -26<=k<=26, -15<=l<=16 Reflections collected Independent reflections 6037 [R(int) = ] Completeness to theta = % Absorption correction Empirical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6037 / 0 / 375 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 S16

17 Molecular structure of the cation of 4a, hydrogen atoms are omitted for clarity; ellipsoids are set at 50%. Molecular structure of the cation of 5aa, hydrogen atoms are omitted for clarity; ellipsoids are set at 50%. There is a 50:50 carbon:nitrogen disorder at C2 and the symmetry related position C2A S17

18 Molecular structure of the cation of 5ba, hydrogen atoms are omitted for clarity; ellipsoids are set at 50%. Molecular structure of the cation of 5bb, hydrogen atoms are omitted for clarity; ellipsoids are set at 50%. There is a 50:50 carbon:nitrogen disorder at C1 S18

19 Molecular structure of 7a, hydrogen atoms are omitted for clarity; ellipsoids are set at 50%. Molecular structure of 7b, hydrogen atoms are omitted for clarity; ellipsoids are set at 50%. S19

20 Cl 4a[Cl] ppm Cl 4a[Cl] ppm S20

21 S ppm a[PF6] ppm a[PF6]

22 ppm aa[] aa[] ppm S22

23 ab[] ppm ab[] ppm S23

24 S ppm ba[] ppm ba[]

25 bb[] ppm bb[] ppm S25

26 a[] ppm a[] ppm S26

27 b[] ppm b[] ppm S27

28 a[] ppm a[] ppm S28

29 S ppm b[] ppm b[]

30 Cp* Rh Cl 7a ppm Cp* Rh Cl 7a ppm S30

31 S ppm Rh Cl Cp* 7b ppm Rh Cl Cp* 7b

32 References [1] Tönnemann J.; Risse J.; Grote Z.; Scopelliti R.; Severin K., Eur. J. Inorg. Chem. 2013, [2] White C.; Thompson P. M.; Maitlis J.; J. Chem. Soc., Dalton Trans. 1977, [3] Boutadla Y.; Davies D. L.; Jones R. C.; Singh K., Chem. Eur. J. 2011, 17, [4] Bruker, Version 6.10 ed., Bruker Inc, Madison, Wisconsin, USA, [5] Farrugia L.; J.; J. Appl. Cryst. 1997, 30, 565 S32

Supporting Information

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