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1 Supporting Information Wiley-VCH Weinheim, Germany

2 A Second Generation Catalyst for Intermolecular Alkene and Alkyne Hydroacylation using -S-Substituted Aldehydes: The Role of a Hemilabile P-O-P Ligand Gemma L. Moxham, Helen E. Randell-Sly, Simon K. Brayshaw, Robert L. Woodward, Andrew S. Weller * and Michael C. Willis * Department of Chemistry, University of Bath, Bath, BA 7AY, UK. General information page S General procedure for hydroacylation reactions using three component catalyst Data for compounds prepared in Table, Entries 1, 6-8, 10 and 11 S3 S3 1 H NMR spectra for compounds prepared in Table, Entries 1, 6-8, 10 and 11 S6 Procedures for preparation of organometallic complexes S11 X-ray crystal data S17 References S4 S1

3 Angew. Chemie Int. Ed. Supporting Information General Information: All manipulations, unless otherwise stated, were performed under an atmosphere of argon, using standard Schlenk-line and glove-box techniques. Glassware was oven dried at 130 C overnight and flamed under vacuum prior to use. CH Cl and pentane were dried over activated alumina, copper and molecular sieves using an MBraun solvent purification system. CD Cl, and CDCl 3 were distilled under vacuum from CaH. Acetone and d 6 -acetone were distilled under vacuum from B O 3. Petrol refers to the fraction of petroleum ether obtained between o C. Microanalyses were performed by the University of Bath Microanalytical Service or by Elemental Microanalysis Limited. Flash chromatography was conducted under medium pressure, using matrix 60 silica. 1 H, 1 H{ 11 B}, 11 B, 11 B{ 1 H} and 31 P{ 1 H} NMR spectra were recorded on Bruker Avance 400 MHz and Bruker Avance 300 MHz spectrometers. Residual protio solvent was used as reference for 1 H and 1 H{ 11 B} NMR spectra (CDCl 3 : = 7.6, CD Cl : = 5.33, d 6 -acetone: =.04, d 8 -toluene: =.09). 11 B, 11 B{ 1 H} and 31 P{ 1 H} spectra were referenced against BF 3.OEt (external) and 85% H 3 PO 4 (external) respectively. Chemical shifts are quoted in ppm. Coupling constants are quoted in Hz. IR spectra were recorded using NaCl discs. Gas chromatography was performed using a Perkin-Elmer GC, helium carrier gas (1 psi), injection volume 0. µl, oven temperature ramped between 60 and 180 C and a flame ionisation detector. Data was analysed using the TurboChrom software package. The starting materials Cs[CB 11 H 6 Cl 6 ], 1 Cs[CB 11 H 6 Br 6 ], 1 and [Rh(NBD)Cl] were prepared by published literature methods or variations thereof. The products obtained in Table, Entries 1-5 3,4 and entries 9 5 and 1, 6 provided data consistent with that in the literature. S

4 Angew. Chemie Int. Ed. Supporting Information General procedure for intermolecular hydroacylation reactions using catalyst generated from [Rh(cod)Cl], DPEphos and AgClO 4 : Exemplified by the preparation of methyl 6-(methylthio)-4-oxohexanoate (Table, Entry 1) SMe O OMe O Acetone (1.5 ml) was added under argon to [Rh(COD)Cl] (3.7 mg, mmol) followed by silver perchlorate (3.1 mg mmol). The resulting mixture was stirred at room temperature for 10 minutes. After this time DPEphos (8 mg, 0.15 mmol) was added and the mixture continued to be stirred for a further 15 minutes. Subsequently 3-(methylthio)propionaldehyde (30 µl, 0.3 mmole) was added immediately followed by methyl acrylate (54 µl, 0.6 mmol ). The resulting solution was heated and stirred at 55 C for 90 minutes. The solution was then cooled to room temperature, reduced in vacu and purified by flash chromatography (1:4 EtOAc: Hexane) giving the title compound as a colourless oil (4 mg, 74% yield); H (300 MHz, CDCl 3 ) 3.68 (3H, s), (6H, m),.61 (H t, J 6.3 Hz),.11 (3H, s); C (101 MHz, CDCl 3 ) 07.1, 173., 51.9, 4.5, 37.3, 7.9, 7.7, Data consistant to that in the literature. 1 (E)-9-chloro--(ethylthio)non-5-en-4-one (Table, Entry 6) SEt O Cl Me The general procedure for the hydroacylation reaction was followed employing [Rh(COD)Cl] (1.8 mg, mmol), silver perchlorate (1.5 mg mmol), DPEphos (4 mg, mmol), 3-(ethylthio)butanal (0 µl, 0.15 mmole) and 5- chloro-1-pentyne (3 µl, 0.30 mmol). Heated at 55 C overnight. Flash chromatography (1:4 EtOAc: Hexane) yielded the title compound as a yellow oil (34 mg, 97% yield); ); " max (film) /cm , 1668, 1416, 167, 744; H (300 MHz; CDCl 3 ) 6.75 (1H, dt, J 15.9, 6.9), 6.10 (1H, dt, J 15.9, 1.5), 3.49 (H, t, J 6.4), (1H, m),.79 (1H, dd, J 16.3, 5.6),.60 (1H, dd, J 16.3, 8.3),.51 (H, q, J 7.4), (H, m), (H, m), 1.3 (3H, d, J 6.7), 1.19 (3H, t, J 7,4); C (75 MHz; CDCl 3 ) 197.9, 145.4, 131.1, 47.4, 43.8, 34.7, 30.5, 9.3, 4.6, 1.4, 14.5; m/z (EI+) 34 (10 %, M+), 00, 17, 131, 89; found [M+H] + C 11 H 0 ClOS requires (E)-5-(ethylthio)--methyl-1-phenylhex-1-en-3-one (Table, Entry 7) S3

5 Angew. Chemie Int. Ed. Supporting Information SEt O Me Me The general procedure for the hydroacylation reaction was followed employing Rh(COD)Cl] (1.8 mg, mmol), silver perchlorate (1.5 mg mmol), DPEphos (4 mg, mmol), 3-(ethylthio)butanal (0 µl, 0.15 mmole) and 1- phenyl-1-propyne (38 µl, 0.30 mmol). Heated at 55 C for 30 hours. Flash chromatography (1:4 EtOAc: Hexane) yielded the title compound as a yellow oil (7 mg, 73% yield); " max (film) /cm , 1796, 1663, 1473, 908; H (300 MHz; CDCl 3 ) 7.45 (1H, br. s), (1H, m), 3.06 (1H, dd, J 16.4, 5.4),.87 (1H, dd, J 16.4, 8.4),.54 (H, q, J 7.4),.01 (3H, d, J 1.3), 1.7 (3H, d, J 6.7), 1.1 (3H, t, J 7.4); C (75 MHz; CDCl 3 ) 00.7, 139.5, 138.0, 136., 14.4, 45.5, 36.0, 5.3,.1, 15., 13.6; m/z (EI+) 48 ( %, M+), 186, 115, 91; found [M+H] + C 15 H 1 OS requires (Ethylthio)dodecan-4-one (Table, Entry 8) SEt O Me The general procedure for the hydroacylation reaction was followed employing Rh(COD)Cl] (1.8 mg, mmol), silver perchlorate (1.5 mg mmol), DPEphos (4 mg, mmol), 3-(ethylthio)butanal (0 µl, 0.15 mmole) and 1- octene (47 µl, 0.3 mmol). Heated at 55 C for 48 hours. Flash chromatography (1:9 EtOAc: Hexane) yielded the title compound as a yellow oil (6 mg, 61% yield); " max (film) /cm , 1796, 1663, 1473, 908; H (300 MHz; CDCl 3 ) (1H, m), (1H, m),.64 (1H, dd, J 16.7, 5.9), (4H, m), (H, m), (16H, m), 0.81 (3H, t, J 6.8); C (75 MHz; CDCl 3 ) 09.7, 50.4, 44.1, 35.1, 3., 9.8, 9.6, 9.5, 5.1, 4.1, 3.1,.1, 15., 14.5; m/z (CI+, NH 3 ) 6 (50 %, M+ NH 3 ), 04, 00, 183; found [M+H] + C 14 H 9 OS requires (E)-7-Chloro-1-(1,3-dithian--yl)hept-3-en--one (Table, Entry 10) S4

6 Angew. Chemie Int. Ed. Supporting Information O S S Cl The general procedure for the hydroacylation reaction was followed employing Rh(COD)Cl] (1.8 mg, mmol), silver perchlorate (1.5 mg mmol), DPEphos (4 mg, mmol), -(1,3-dithian--yl)acetaldehyde (5 mg, 0.15 mmole) and 5-chloro-1-pentyne (3 µl, 0.30 mmol). Heated at 55 C for 4 hours. Flash chromatography (1:9 EtOAc: Hexane) yielded the title compound as a yellow oil (34 mg, 87% yield); " max (film) /cm , 1791, 1463, 1375, 1093, 908, 78; H (300 MHz; CDCl 3 ) 6.79 (1H, dt, J 15.9, 6.9), 6.1 (1H, dt, J 15.9, 1.5), 4.48 (1H, t, J 7.0), 3.49 (H, t, J 6.4), (6H, m), (H, m), (1H, m), (3H, m); C (75 MHz; CDCl 3 ) 195.4, 146.7, 131.1, 45.3, 44.0, 41.7, 30.7, 30.4, 9.6, 5.4; m/z (EI+) 64 (8 %, M+), 01, 133, 119; found [M+H] + C 11 H 18 ClOS requires (E)-1-(1,3-Dithian--yl)-3-methyl-4-phenylbut-3-en--one (Table, Entry 11) S S O The general procedure for the hydroacylation reaction was followed employing Rh(COD)Cl] (1.8 mg, mmol), silver perchlorate (1.5 mg mmol), DPEphos (4 mg, mmol), -(1,3-dithian--yl)acetaldehyde (5 mg, 0.15 mmole) and 1-phenyl-1-propyne (38 µl, 0.30 mmol). Heated at 55 C for 4 hours. Flash chromatography (1:9 EtOAc: Hexane) yielded the title compound as a yellow oil (34 mg, 8% yield); " max (film) /cm , 1663, 111, 908; H (300 MHz; CDCl 3 ) 7.45 (1H, br. s), (5H,m), 4.57 (H, t, J 7.0), 3.14 (3H, d, J 7.0), (4H, m), (1H, m),.0 (3H, d, J 1.4), (1H, m); C (75 MHz; CDCl 3 ) 197.6, 139.7, 137.5, 135.6, 19.9 ( CH), 18.8, 18.5 ( CH), 4.8, 4.4, 30.4 ( CH ), 5.4, 13.; m/z (EI+) 78 (30 %, M+), 145, 115, 91; found [M+H] + C 15 H 19 OS requires S5

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12 All complexes containing the DPEphos ligand were partnered with each of the anions [CB 11 H 6 Cl 6 ] -, [CB 11 H 6 Br 6 ] -, [BAr F 4] -, [PF 6 ] - and [ClO 4 ] -. The anion sources used were Cs[CB 11 H 6 X 6 ], Na[BAr F 4], Ag[PF 6 ] and Ag[ClO 4 ]. The compounds which formed have identical NMR data except for those signals pertaining to the anion. The signals for each anion are as follows: [CB 11 H 6 Cl 6 ] - 1 H NMR (/ppm CD Cl ).1 (br s, 1H, cage CH). 11 B NMR (/ppm CD Cl ) 1.5 (br s, 1B, BCl), -5.1 (br s, 5B, BCl), -3.4 (d, J(HB) 164 Hz, 5B, BH). [CB 11 H 6 Br 6 ] - 1 H NMR (/ppm CD Cl ).54 (br s, 1H, cage CH). 11 B NMR (/ppm CD Cl ) -1.8 (s, 1B, BBr), (s, 5B, BBr), -0. (d, J(HB) 171 Hz, 5B, BH). [BAr F 4] - 1 H NMR (/ppm CD Cl ) 7.71 (m, 8H, ArH), 7.55 (s, 4H, ArH). 11 B NMR (/ppm CD Cl ) -5.9 (s). [PF 6 ] - 31 P{ 1 H} NMR (/ppm d 6 -acetone) (sept, J(FP) 707 Hz). Preparation of [(DPEphos)Rh(NBD)][X] A Schlenk tube was charged with [Rh(NBD)Cl] (0.049 g, 1.05 x10-4 moles) and DPEphos (0.113 g,.1 x10-4 moles). Methanol (5 cm 3 ) was added and the mixture was stirred until all the solid had dissolved (ca. 30 mins). To the yellow solution, a salt of the required anion (.1 x 10-4 moles) was added. After stirring for an hour a yellow/orange precipitate had formed. The methanol was removed in vacuo and the solid was partially S11

13 dissolved in CH Cl. The mixture was filtered and pentane was added to the filtrate. The mixture was stored at -18 C overnight to give the product as orange crystals. Yield: 54-77% depending on anion used. 1 H NMR (/ppm CD Cl ) (m, 8H, ArH), 4.9 (s, 4H, NBD), 3.85 (s, H, NBD), 1.51 (s, H, NBD). 31 P{ 1 H} NMR (/ppm CD Cl ) (d, J(RhP) 159 Hz). X = [CB 11 H 6 Cl 6 ] - Yield: 56 % Calculated: C 46.7 %, H 3.80 % Found: C %, H 3.84 % X = [CB 11 H 6 Br 6 ] - Yield: 54 % Calculated: C %, H 3.11 % Found: C %, H 3.04 % X = [CB 11 H 6 I 6 ] - Yield: 60 % Calculated: C %, H.57 % Found: C %, H.71 % X = [BAr F 4] - Yield: 77 % Calculated: C %, H 3.01 % Found: C %, H.89 % Preparation of [(DPEphos)Rh(acetone) ][CB 11 H 6 Cl 6 ] (A) A solution of [(DPEphos)Rh(NBD)][CB 11 H 6 Cl 6 ] (1. x10-5 moles) in d 6 -acetone (0.5 cm 3 ) was freeze thaw degassed and back filled with hydrogen at -196 C. On warming to room temperature there was a colour change from orange to red. The product was characterised in situ by NMR spectroscopy. Crystal suitable for X-ray diffraction were obtained by diffusion of pentane into a solution of the complex in acetone. S1

14 1 H NMR (/ppm d 6 -acetone) (m, 8H, ArH). 31 P{ 1 H} NMR (/ppm d 6 -acetone) (d, J(RhP) 08.6 Hz). Preparation of [(DPEphos)Rh(COCH CH SMe)H][CB 11 H 6 Cl 6 ] (B) To a solution of [(DPEphos)Rh(acetone) ][X] (1. x10-5 moles) in d 6 -acetone (0.5 cm 3 ) 3-(methylthio)propionaldehyde (.4 µl,.4 x10-5 moles) was added. There was an immediate colour change from red to yellow. The product was characterised in situ by NMR spectroscopy. 1 H NMR (/ppm d 6 -acetone 98 K) (m, 8H ArH), 1.56 (s, 3H, CH 3 S) (dt, J(RhH) 3. Hz, J(PH) ~ 1 Hz, 1H, RhH). 31 P{ 1 H} NMR (/ppm d 6 -acetone 98 K) 6.0 (d, J(RhP) 17 Hz). 1 H NMR (/ppm d 6 -acetone 180 K) selected -8.6 (d t, J(RhH) 3. Hz, J(PH) ~1 Hz, 1H, RhH). 31 P{ 1 H} NMR (/ppm d 6 -acetone 180 K) 6.8, 5.9 (AB doublet, J(RhP) 15 Hz, J(PP) 303 Hz). Preparation of [(DPEphos)Rh(CO)(EtSMe)H][CB 11 H 6 Cl 6 ] (E) A solution of compound B in acetone was allowed to stand at room temperature for three days. 1 H NMR (/ppm d 6 -acetone 98 K) (m, 8H, ArH),.66 (q, J(HH) 7 Hz, H, CH ),.19 (s, 3H, CH 3 ), 1.1 (t, J(HH) 7 Hz, 3H, CH 3 ). 31 P{ 1 H} NMR (/ppm d 6 -acetone 98 K) 18.5 (br s). 31 P{ 1 H} NMR (/ppm d 6 -acetone 00 K) 0.7 (br dd, J(RhP) 150 Hz, J(PP) ~30 Hz), 15.9 (br dd, J(RhP) 15 Hz, J(PP) ~30 Hz). X-ray quality crystals of E could not be obtained using the [CB 11 H 6 Cl 6 ] - anion. The analogous compound was prepared using the [CB 11 H 6 Br 6 ] - anion in acetone solution and layered with pentane to yield crystals suitable for x-ray diffraction studies. S13

15 Preparation of [(DPEphos)Rh(COCH CH SMe)H(MeCN)][CB 11 H 6 Cl 6 ] (F) 5 equivalents of acetonitrile were added to a solution of [(DPEphos)Rh(COCH CH SMe)H][CB 11 H 6 Cl 6 ] in acetone to give [(DPEphos)Rh(COCH CH SMe)H(MeCN)][CB 11 H 6 Cl 6 ]. Crystals suitable for X-ray diffraction were obtained by diffusion of pentane into a solution of the complex in acetone. 1 H NMR (/ppm d 6 -acetone) selected (m, 8H, ArH), (br t), (br). 31 P{ 1 H} NMR (/ppm d 6 -acetone) 33.9 (d, J(RhP) 150 Hz), 30.9 (dd, J(RhP) 150 Hz, J(PP) 16 Hz), 7.9 (d, J(RhP) 65 Hz), 7.0 (dd, J(RhP) 65 Hz, J(PP) 16 Hz). Indicates major isomer (70 %) Indicates minor isomer (30 %) Preparation of [(DPEphos)Rh(CO(CH ) SMe)H(MeS(CH ) CHO)][CB 11 H 6 Cl 6 ] (G) 5 equivalents of aldehyde were added to a solution of [(DPEphos)Rh(COCH CH SMe)H][CB 11 H 6 Cl 6 ] in acetone to give [(DPEphos)Rh(COCH CH SMe)H(MeSCH CH CHO)][CB 11 H 6 Cl 6 ]. (98 K NMR data is the same as that observed for compound B at 98 K.) 1 H NMR (/ppm d 6 -acetone 00 K) 9.55 (s, CHO), (m, 8H, ArH), (br m, RhH). N.B. hydride resonances cannot be resolved as the signals for the two isomers overlap. 31 P{ 1 H} NMR (/ppm d 6 -acetone 00 K) 31. (dd, J(RhP) 148 Hz, J(PP) 17.3 Hz), 30.9 (dd, J(RhP) 149 Hz, J(PP) 17.8 Hz),.84 (dd, J(RhP) 6 Hz, J(PP) 17.8 Hz), 1.0 (dd, J(RhP) 61Hz J(PP) 17.3 Hz). Indicates first isomer (50 %) Indicates second isomer (50 %) Preparation of [(PSP)Rh(NBD)][X] (H) A Schlenk tube was charged with [Rh(NBD)Cl] (0.050 g, 1.08 x10-4 moles) and S{(C 6 H 4 )PPh } (0.10 g,.17 x10-4 moles). Methanol (5 cm 3 ) was added and the S14

16 mixture wa stirred until all the solid had dissolved (ca. 30 mins). To the yellow solution, a salt of the required anion (.17 x 10-4 moles) was added. After stirring for an hour a yellow/orange precipitate had formed. The methanol was removed in vacuo and the solid was partially dissolved in CH Cl. The mixture was filtered and pentane was added to the filtrate. The mixture was stored at -18 C overnight to give the product as orange crystals. No change was observed on addition of hydrogen to a solution of the complex in acetone. 1 H NMR (/ppm d 6 -acetone) (m, 8H, ArH), 3.89 (br m, 4H, NBD),.96 (s, H, NBD), 1.18 (br m, H, NBD). 31 P{ 1 H} NMR (/ppm d 6 -acetone) 55.5 (d, J(RhP) 15 Hz). Preparation of [(PCP)Rh(NBD)][CB 11 H 6 Br 6 ] A Schlenk tube was charged with [Rh(NBD)Cl] (0.043 g, 9.3 x10-5 moles) and CH {(C 6 H 4 )PPh } (0.100 g, 1.86 x10-4 moles). Methanol (5 cm 3 ) was added and the mixture was stirred until all the solid had dissolved (ca. 30 mins). To the yellow solution, Cs[CB 11 H 6 Br 6 ] (0.140g 1.86 x 10-4 moles) was added. After stirring for one hour a yellow/orange precipitate had formed. The methanol was removed in vacuo and the solid was partially dissolved in CH Cl. The mixture was filtered and pentane was added to the filtrate. The mixture was stored at -18 C overnight to give the product as orange crystals. 1 H NMR (/ppm CD Cl ) (m, 8H ArH), 6.4 (dt, J(HH) 14.7 Hz, J(HH) 3.9 Hz, 1H, CH of PCP), 4.51 (s, H, NBD), 4.43 (s, H, NBD), 4.33 (d, J(HH) 14.4 Hz, 1H, CH of PCP), 3.95 (s, 1H, NBD), 3.89 (s, 1H, NBD), 1.64 (s, H, NBD) 31 P{ 1 H} NMR (/ppm CD Cl ) 3.0 (d, J(RhP) 167 Hz) Preparation of [(PCP)Rh(acetone) ][CB 11 H 6 Br 6 ] (I) A solution of [(PCP)Rh(NBD)][CB 11 H 6 Br 6 ] (10mg, 7.4 x10-6 moles) in d 6 -acetone (0.5 cm 3 ) was freeze thaw degassed and back filled with hydrogen at -196 C. On warming to S15

17 room temperature there was a colour change from orange to red. The product was characterised in situ by NMR spectroscopy. 1 H NMR (/ppm d 6 -acetone) (m, 8H, ArH) 31 P{ 1 H} NMR (/ppm d 6 -acetone) 41.5 (d, J(RhP) 01.8 Hz) On addition of aldehyde a mixture of products was observed. Preparation of [(DPPE)Rh(NBD)][CB 11 H 6 Br 6 ] A solution of DPPE (0.074 g, 1.86 x10-4 mol) in ethanol was added slowly to a solution of [Rh(NBD)Cl] (0.043 g, 9.3 x10-5 mol) in ethanol. The mixture was stirred for ca. 30 mins. To the yellow solution, Cs[CB 11 H 6 Br 6 ] (0.140 g, 1.86 x 10-4 moles) was added. After stirring for an hour a yellow/orange precipitate had formed. The ethanol was removed in vacuo and the solid was partially dissolved in CH Cl. The mixture was filtered and pentane was added to the filtrate. The mixture was stored at -18 C overnight to give the product as orange crystals. 1 H NMR (/ppm d 6 -acetone) (m, 0H, ArH), 5.49 (m, 4H, NBD), 4.6 (s, H, NBD),.57 (m, 4H, ethane bridge), 1.8 (s, H, NBD). 31 P{ 1 H} NMR (/ppm d 6 -acetone) 57.1 (d, J(RhP) 157 Hz). Preparation of [(DPPE)Rh(acetone) ][CB 11 H 6 Br 6 ] A solution of [(DPPE)Rh(NBD)][CB 11 H 6 Br 6 ] (7.4 x10-6 moles) in d 6 -acetone (0.5 cm 3 ) was freeze thaw degassed and back filled with hydrogen at -196 C. On warming to room temperature there was a colour change from orange to red. The product was characterised in situ by NMR spectroscopy. 1 H NMR (/ppm d 6 -acetone) (m, 0H, ArH),.35 (m, 4H, ethane bridge). 31 P{ 1 H} NMR (/ppm d 6 -acetone) 79.1 (d, J(RhP) 01 Hz). S16

18 Preparation of [(DPPE)Rh(COCH CH SMe)H][CB 11 H 6 Br 6 ] To a solution of [(DPPE)Rh(acetone) ][CB 11 H 6 Br 6 ] (1. x10-5 moles) in d 6 -acetone (0.5 cm 3 ) 3-(methylthio)propionaldehyde (.4 µl,.4 x10-5 moles) was added. There was a colour change from red to yellow. The product was characterised in situ by NMR spectroscopy. Selected 1 H NMR (/ppm d 6 -acetone) (m, 0H, ArH). 31 P{ 1 H} NMR (/ppm d 6 -acetone) 57.9 (d, J(RhP) 135 Hz), 38.7 (d, J(RhP) 70 Hz). Within 1 hour at room temperature the complex had decomposed to a mixture of products including the decarbonylation product (identified by mass spectrometry). X-ray Crystallography Structure solution, and full matrix least squares refinement on F (all data) was performed using SHELX 7. under the WinGX 1.70 package, 8. after using SORTAV 9. for absorbtion correction where indicated. In all structures, some disorder of the anion was evident. A, F and H were crystallized as their hexachlorocarborane salts, while E was crystallized as its hexabromocarborane salt. For A, one of the coordinated acetone ligands was disordered over two sites in the ratio 0.85 : 0.15, with concommitant positional disorder of the lattice acetone molecules. The lower occupancy coordinated acetone was modelled isotropically and all solvent acetone units were refined with geometry restraints. For F, the residual electron density in a solvent accessible void was accounted for using the Platon program SQEEZE. 10. CCDC contain additional supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via S17

19 ORTEP plot (50% probability ellipsoids) of the cationic portion of A. ORTEP plot (50% probability ellipsoids) of the cationic portion of F. S18

20 ORTEP plot (50% probability ellipsoids) of the cationic portion of E. ORTEP plot (50% probability ellipsoids) of the cationic portion of H. S19

21 Angew. Chemie Int. Ed. Supporting Information Table S1. Crystal data and structure refinement for A. Empirical formula C46 H51.87 B11 Cl6.13 O4 P Rh Formula weight Temperature Wavelength Crystal system 150() K A Triclinic Space group P -1 Unit cell dimensions a = (1) A alpha = (3) deg. b = (1) A beta = (3) deg. c = (1) A gamma = (3) deg. Volume 80.33(3) A^3 Z, Calculated density, Mg/m^3 Absorption coefficient mm^-1 F(000) Crystal size Theta range for data collection 0.30 x 0.0 x 0.0 mm 3.53 to 8.48 deg. Limiting indices -18<=h<=18, -18<=k<=18, - 3<=l<=3 Reflections collected / unique 5443 / [R(int) = ] Completeness to theta = % Absorption correction equivalents Semi-empirical from Max. and min. transmission and 0.80 Refinement method F^ Full-matrix least-squares on Data / restraints / parameters / 64 / 703 Goodness-of-fit on F^ Final R indices [I>sigma(I)] R1 = 0.031, wr = R indices (all data) R1 = 0.048, wr = Largest diff. peak and hole and e.a^-3 S0

22 Angew. Chemie Int. Ed. Supporting Information Table S. Crystal data and structure refinement for F. Empirical formula Rh S C46 H50.9 B11 Cl6.08 N O3 P Formula weight Temperature Wavelength Crystal system 150() K A Monoclinic Space group C /c Unit cell dimensions a = (3) A alpha = 90 deg. b = 11.31(1) A beta = (7) deg. c = 3.5(3) A gamma = 90 deg. Volume () A^3 Z, Calculated density 8, 1.36 Mg/m^3 Absorption coefficient mm^-1 F(000) 4858 Crystal size Theta range for data collection 0.8 x 0.3 x 0.10 mm 3.49 to 6.3 deg. Limiting indices -43<=h<=43, -14<=k<=14, - 40<=l<=40 Reflections collected / unique / [R(int) = ] Completeness to theta = % Absorption correction None Max. and min. transmission and Refinement method F^ Full-matrix least-squares on Data / restraints / parameters / 76 / 837 Goodness-of-fit on F^ Final R indices [I>sigma(I)] R1 = , wr = R indices (all data) R1 = , wr = Largest diff. peak and hole and e.a^-3 S1

23 Angew. Chemie Int. Ed. Supporting Information Table S3. Crystal data and structure refinement for E. Empirical formula C41 H4 B11 Br6 O P Rh S Formula weight Temperature Wavelength Crystal system 150() K A Monoclinic Space group C /c Unit cell dimensions a = (4) A alpha = 90 deg. b = 13.48() A beta = (7) deg. c = (5) A gamma = 90 deg. Volume (3) A^3 Z, Calculated density 8, Mg/m^3 Absorption coefficient mm^-1 F(000) 580 Crystal size Theta range for data collection Limiting indices 0.45 x 0.30 x 0.08 mm 3.54 to 7.58 deg. -3<=h<=3, -17<=k<=17, -39<=l<=39 Reflections collected / unique 3913 / [R(int) = ] Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F^ Data / restraints / parameters / 0 / 578 Goodness-of-fit on F^ Final R indices [I>sigma(I)] R1 = , wr = R indices (all data) R1 = 0.077, wr = Largest diff. peak and hole.193 and e.a^-3 S

24 Angew. Chemie Int. Ed. Supporting Information Table S4. Crystal data and structure refinement for H. Empirical formula C44 H41.9 B11 Cl6.08 P Rh S Formula weight Temperature Wavelength Crystal system Space group 150() K A Orthorhombic P b c a Unit cell dimensions a = (1) A alpha = 90 deg. b = (1) A beta = 90 deg. c = (1) A gamma = 90 deg. Volume (8) A^3 Z, Calculated density 8, Mg/m^3 Absorption coefficient 0.89 mm^-1 F(000) 444. Crystal size Theta range for data collection 0.45 x 0.35 x 0.0 mm 3.49 to 33.1 deg. Limiting indices -31<=h<=30, -8<=k<=8, - 38<=l<=38 Reflections collected / unique / 1848 [R(int) = ] Completeness to theta = % Absorption correction None Max. and min. transmission and Refinement method F^ Full-matrix least-squares on Data / restraints / parameters 1848 / 4 / 611 Goodness-of-fit on F^ Final R indices [I>sigma(I)] R1 = , wr = R indices (all data) R1 = , wr = Largest diff. peak and hole and e.a^-3 S3

25 Angew. Chemie Int. Ed. Supporting Information References 1. T. Jelinek, J. Plesek, S. Hermanek, B. Stibr, Collect. Czech. Chem. Commun. 1986, 51, E. W. Abel, M. A. Bennett, G. Wilkinson, J. Chem. Soc. 1959, M. C. Willis, S. J. McNally, P. J. Beswick, Angew. Chem. Int. Ed. 004, 43, M. C. Willis, H. E. Randell-Sly, R. L. Woodward, S. J. McNally, G. Currie, J. Org. Chem. 005, 71, M. C. Willis, H. E. Randell-Sly, R. L. Woodward, G. Currie, Org. Lett. 005, 7, D. Stossel, T. H. Chan, J. Org. Chem. 1988, 53, WinGX-1.70: L. J. Farrugia, J. Appl. Crystallogr., 1999, 3, SHELXL97 - A program for crystal structure refinement. G. M. Sheldrick, SORTAV: R. H. Blessing, Acta. Crystallogr. A, 1995, 51, Platon: A. L. Spek, J.Appl.Cryst. 003, 36, 7. S4

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