Supporting Information for. Controlled Hydrosilylation of Carbonyls and Imines Catalyzed by a Cationic Aluminum Alkyl Complex

Transcription

1 Supporting Information for Controlled Hydrosilylation of Carbonyls and Imines Catalyzed by a Cationic Aluminum Alkyl Complex Jürgen Koller and Robert G. Bergman* Department of Chemistry, University of California, Berkeley, CA I. Experimental Section General Procedures. Unless otherwise noted, all reactions and manipulations were performed in an inert atmosphere (N 2 ) glovebox, or using standard Schlenk and high vacuum-line techniques. Glassware was dried overnight at 150 C before use. 1 H and 13 C NMR spectra were recorded at room temperature (except where noted) on Bruker AV 300 MHz, AVB 400 MHz, AVQ 400 MHz, or DRX 500 MHz spectrometers using residual protons of deuterated solvents for reference. Elemental analyses were performed at the University of California, Berkeley, Microanalytical Facility, on a Perkin-Elmer 2400 Series II CHNO/S analyzer. High resolution mass spectral data were obtained at the QB3 Mass Spectrometry Facility operated by the College of Chemistry, University of California, Berkeley. Low resolution mass spectral data were obtained on a 6890N gas chromatograph system coupled to a 5973N mass selective detector (Agilent Technologies). Sealed NMR tubes were prepared by attaching the NMR tube directly to a Kontes high-vacuum stopcock via a Cajon Ultra-Torr reducing union followed by flamesealing on a vacuum-line. Materials. Unless otherwise noted, reagents were purchased from commercial suppliers and used without further purification. Pentane, hexanes, diethyl ether, and methylene chloride were purified by passing the degassed solvents through a column of activated alumina (type A2, size 12 32, Purifry Co.) under nitrogen pressure followed by additional sparging with N 2 prior to use. B(C 6 F 5 ) 3 was purchased from Aldrich and sublimed prior to use. CDCl 3 (Cambridge Isotope Laboratories), triethylamine, butan-2-one, 3-methylbutan-2-one, hex-5-en-2-one, cyclohex-2-enone, 4,4-dimethylcyclohex-2-enone, 1-cyclopropylethanone, acetophenone, cyclohexanone, δ-valerolactone, benzaldehyde, propionaldehyde, and cinnamaldehyde were distilled from CaH 2 and stored over activated 3 Å molecular sieves. N-Benzylidene-4- methylbenzenesulfonamide 1 and DSiEt 3 (D, 99.6%) 2 were prepared according to literature procedures. - S1 -

2 Tp*AlMe 2 (1). 3,4 A stirred solution of KTp* (5.00 g, 14.9 mmol) in CH 2 Cl 2 (100 ml) was cooled to 0 C and AlClMe 2 (20 ml, 0.9 M solution in heptane, 17.9 mmol) was added dropwise under vigorous stirring. The mixture was slowly warmed to room temperature and stirred for another 18 h. The resulting suspension was filtered through a pad of celite to remove KCl. All volatiles were removed in vacuo to yield analytically pure 1 as a white solid. Yield: 5.19 g (99%, 14.7 mmol). Compound 1 may be further purified by sublimation at 0.1 torr/100 C. Single crystals were grown from a concentrated diethyl ether solution at -35 C. 1 H NMR (CDCl 3, 400 MHz): δ 5.81 (s, 3H, py), 2.29 (s, 9H, CH 3 ), 2.28 (s, 9H, CH 3 ), (s, 6H, AlCH 3 ). 13 C NMR (CDCl 3, 101 MHz): δ (s, py), (s, py), (s, py), (s, CH 3 ), (s, CH 3 ), (s, AlCH 3 ). Anal. calcd for C 17 H 28 N 6 AlB: C, 57.64; H, 7.97; N, 23.72; found: C, 57.62; H, 7.62; N, [Tp*AlMe][MeB(C 6 F 5 ) 3 ] (2). To a stirred solution of 1 (1.00 g, 2.82 mmol) in CH 2 Cl 2 (7 ml) was added a solution of B(C 6 F 5 ) 3 (1.45 g, 2.82 mmol) in 7 ml of CH 2 Cl 2 via pipet. The clear mixture was stirred at room temperature for 30 min. The solution was then filtered, layered with 20 ml of pentane, and subsequently cooled to -35 C. Pure 2 was isolated via filtration as large colorless crystals which were dried in vacuo. Yield: 1.92 g (78%, 2.22 mmol). 1 H NMR (CDCl 3, 500 MHz): δ 5.95 (s, 3H, py), 2.40 (s, 9H, CH 3 ), 2.34 (s, 9H, CH 3 ), 0.41 (bs, 3H, BCH 3 ), 0.26 (s, 3H, AlCH 3 ). 13 C NMR (CDCl 3, 126 MHz): δ (s, py), (s, py), (s, py), (s, CH 3 ), (s, CH 3 ). Anal. calcd for C 35 H 28 N 6 AlB 2 F 15 : C, 48.53; H, 3.26; N, 9.70; found: C, 47.08; H, 3.02; N, HRMS (ESI): calcd for [C 15 H 23 N 6 AlBO] + : , found [Note: Elemental analysis of 2 was consistently low in carbon, even when highly crystalline material was used. The attempted HRMS (ESI) experiments resulted in the observation of only the corresponding hydrolysis product [Tp*AlOH] + even after rigorous sample preparation]. [Tp*AlMe][I 3 ](CH 2 Cl 2 ) (3). To a stirred solution of I 2 (1.43 g, 5.64 mmol) in CH 2 Cl 2 (10 ml) was added a solution of 1 (1.00 g, 2.82 mmol) in 10 ml of CH 2 Cl 2 via pipet under vigorous stirring. The deep red mixture was stirred at room temperature for 2 days. The solution was filtered and cooled to -35 C resulting in the formation of analytically pure 3 as orange crystals which were isolated by filtration and dried in vacuo. Yield: 1.26 g (56%, 1.57 mmol). Single crystals were grown from a CH 2 Cl 2 solution at -35 C. 1 H NMR (CDCl 3, 500 MHz): δ 6.05 (s, 3H, py), 5.30 (s, 2H, CH 2 Cl 2 ), 2.51 (s, 9H, CH 3 ), 2.48 (s, 9H, CH 3 ), 0.36 (s, 3H, AlCH 3 ). 13 C NMR (CDCl 3, 101 MHz): δ (s, py), (s, py), (s, py), (s, CH 2 Cl 2 ), (s, CH 3 ), (s, CH 3 ). Anal. calcd for C 17 H 27 N 6 AlBCl 2 I 3 : C, 25.37; H, 3.38; N, 10.44; found: C, 25.76; H, 3.23; N, S2 -

3 1 H NMR Data 1 H NMR Compound 1 - S3 -

4 1 H NMR Compound 2 - S4 -

5 1 H NMR Compound 3 - S5 -

6 II. Hydrosilylation Experiments General Hydrosilylation Procedure. In a typical experiment, a J. Young NMR tube was charged with a solution of 2 dissolved in 1.0 ml of CDCl 3 and a known amount of hexamethylbenzene (internal standard). To this solution, the respective substrate (1.0 mmol) and HSiEt 3 (1.1 mmol) were added via pipet. The NMR tube was then sealed with a Teflon cap and heated at 100 C. The reaction progress was followed by 1 H NMR spectroscopy until quantitative conversion of the substrate was achieved. Subsequently, the reaction mixture was directly charged onto a short silica column and chromatographed using a mixture of hexane and NEt 3 (2%, v/v). The solvent was removed under reduced pressure to yield the pure silyl ethers as typically colorless oils. Select low boiling silyl ethers (such as 4f) were vacuum distilled (in near quantitative yields 5 ) to ensure the absence of NMR and GC/MS silent impurities. Triethyl(propoxy)silane (4a). Colorless oil. Yield: 134 mg (77%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ 3.56 (t, 2H, J H-H = 6.7 Hz, OCH 2 ), 1.55 (m, 2H, CH 2 ), 0.96 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.89 (t, 3H, J H-H = 7.4 Hz, CH 3 ), 0.60 (q, 6H, J H-H = 7.9 Hz, SiCH 2 CH 3 ). GC (Retention time): 8.14 min. MS (EI, +ve): m/z 145 [M Et] +. (Cinnamyloxy)triethylsilane (4b). Pale yellow oil. Yield: 180 mg (73%, mmol). 1 H NMR (CDCl 3, 300 MHz): δ (m, 4H, Ph), (m, 1H, Ph), 6.63 (d, 1H, J H-H = 15.9 Hz, PhCH), 6.32 (dt, 1H, J H-H = 15.8, 5.2 Hz, CH), 4.37 (dd, 2H, J H-H = 5.2, 1.7 Hz, CH 2 ), 1.02 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.68 (q, 6H, J H-H = 8.2 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 248 [M] +, 219 [M Et] [M Et] +. (Benzyloxy)triethylsilane (4c). Colorless oil. Yield: 221 mg (99%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ (m, 4H, Ph), (m, 1H, Ph), 4.75 (s, 2H, CH 2 ), 0.99 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.67 (q, 6H, J H-H = 7.9 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z - S6 -

7 Triethyl(1-phenylethoxy)silane (4d). Colorless oil. Yield: 191 mg (81%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ (m, 4H, Ph), (m, 1H, Ph), 4.88 (q, 1H, J H-H = 6.4 Hz, CHOSiEt 3 ), 1.45 (d, 3H, J H-H = 6.4 Hz, CH 3 ), 0.93 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), (m, 6H, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 235 [M] +, 207 [M Et] +. (Bis(4-chlorophenyl)methoxy)triethylsilane (4e). Colorless oil. Yield: 364 mg (99%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ 7.29 (bs, 8H, Ph), 5.71 (s, 1H, CHOSiEt 3 ), 0.90 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.59 (q, 6H, J H-H = 7.9 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 337 [M Et] +, 235 [M OSiEt 3 ] +, 199 [M SiEt 3 Cl] +, 165 [M OSiEt 3 Cl Cl] +. sec-butoxytriethylsilane (4f). Colorless oil. Yield: 150 mg (80%, mmol). 1 H NMR (CDCl 3, 300 MHz): δ 3.71 (m, 1H, CHOSiEt 3 ), (m, 2H, CH 2 ), 1.13 (d, 3H, J H-H = 6.1 Hz, CH 3 ), 0.96 (t, 9H, J H-H = 7.1 Hz, SiCH 2 CH 3 ), 0.88 (t, 3H, J H-H = 7.4 Hz, CH 3 ), 0.60 (q, 6H, J H-H = 7.7 Hz, SiCH 2 CH 3 ). GC (Retention time): 8.73 min. MS (EI, +ve): m/z 188 [M] +, 159 [M Et] +. Triethyl((3-methylbutan-2-yl)oxy)silane (4g). Colorless oil. Yield: 184 mg (91%, mmol). 1 H NMR (CDCl 3, 300 MHz): δ 3.55 (sept, 1H, J H-H = 6.1 Hz, CH(CH 3 ) 2 ), (m, 1H, CHOSiEt 3 ), 1.07 (d, 3H, J H-H = 6.2 Hz, CH 3 ), 0.96 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.86 (dd, 6H, J H-H = 6.8, 3.6 Hz, CH(CH 3 ) 2 ), 0.59 (q, 6H, J H-H = 7.5 Hz, SiCH 2 CH 3 ). GC (Retention time): 9.50 min. MS (EI, +ve): m/z 201 [M] +, 173 [M Et] +. (1-Cyclopropylethoxy)triethylsilane (4h). Colorless oil. Yield: 169 mg (84%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ 3.22 (m, 1H, CHOSiEt 3 ), 1.23 (d, 3H, J H-H = 6.1 Hz, CH 3 ), 0.96 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), (m, 1H, CH), 0.59 (q, 6H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), (m, 2H, CH 2 ), (m, 1H, CH 2 ), (m, 1H, CH 2 ),. GC (Retention time): min. MS (EI, +ve): m/z 199 [M] +, 171 [M Et] +, 143 [M Et Et] +. Triethyl(hex-5-en-2-yloxy)silane (4i). Colorless oil. Yield: 198 mg (93%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ 5.82 (ddt, 1H, J H-H = 16.9, 10.2, 6.6 Hz, CH 2 =CH), 4.97 (m, 2H, CH 2 =CH), 3.81 (m, 1H, CHOSiEt 3 ), (m, 2H, CH 2 ), (m, 2H, CH 2 ), 1.15 (d, 3H, J H-H = 6.1 Hz, CH 3 ), 0.96 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.60 (q, 6H, J H-H = 7.7 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 185 [M Et] +. - S7 -

8 (Cyclohexyloxy)triethylsilane (4j). Colorless oil. Yield: 184 mg (86%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ 3.56 (m, 1H, CHOSiEt 3 ), (m, 4H, CH 2 ), 1.52 (m, 1H, CH 2 ), (m, 5H, CH 2 ), 0.96 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.59 (q, 6H, J H-H = 8.0 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 185 [M Et] +. Triethyl((tetrahydro-2H-pyran-2-yl)oxy)silane (4k). Product is not stable on silica column. Product yield was determined in situ via integration of reactant and product signals versus the internal standard. Yield: 50%. 1 H NMR (CDCl 3, 300 MHz): δ 4.30 (m, 1H, CHOSiEt 3 ), 3.62 (m, 2H, OCH 2 ), (m, 2H, CH 2 ), (m, 4H, CH 2 ), 0.90 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.49 (q, 6H, J H-H = 7.9 Hz, SiCH 2 CH 3 ). (Cyclohex-1-en-1-yloxy)triethylsilane (4l). Colorless oil. Yield: 200 mg (94%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ 4.87 (m, 1H, CHOSiEt 3 ), (m, 4H, CH 2 ), (m, 2H, CH 2 ), (m, 2H, CH 2 ), 0.97 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.65 (q, 6H, J H-H = 7.9 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 212 [M] +, 183 [M Et] +. ((4,4-Dimethylcyclohex-1-en-1-yl)oxy)triethylsilane (4m). Pale yellow oil. Yield: 206 mg (91%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ 4.76 (m, 1H, CHOSiEt 3 ), 2.01 (ddd, 2H, J H-H = 8.3, 4.4, 1.7 Hz, CH 2 ), 1.80 (m, 2H, CH 2 ), 1.40 (t, 2H, J H-H = 6.5 Hz, CH 2 ), 0.98 (t, 9H, J H-H = 8.0 Hz, SiCH 2 CH 3 ), 0.92 (s, 6H, CH 3 ), 0.65 (q, 6H, J H-H = 8.0 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 240 [M] +, 211 [M Et] +, 169 [M Me Et] +, 155 [M Et Et Et] +. ((1,3-Diphenylprop-1-en-1-yl)oxy)triethylsilane (4n). Colorless oil. Yield: 321 mg (99%, mmol). 1 H NMR (CDCl 3, 300 MHz): Z isomer: δ (m, 2H, Ph), (m, 8H, Ph), 5.50 (t, 1H, J H-H = 7.2 Hz, CH), 3.78 (d, 2H, J H-H = 7.2 Hz, CH 2 ), 1.13 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.82 (q, 6H, J H-H = 7.6 Hz, SiCH 2 CH 3 ). E isomer: δ (m, 2H, Ph), (m, 8H, Ph), 5.41 (t, 1H, J H-H = 7.9 Hz, CH), 3.65 (d, 2H, J H-H = 7.9 Hz, CH 2 ), 1.13 (t, 9H, J H-H = 7.9 Hz, SiCH 2 CH 3 ), 0.82 (q, 6H, J H-H = 7.6 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 324 [M] +, 295 [M Et] +, 219 [M Et Ph] +. N-benzyl-1,1,1-triethyl-N-phenylsilanamine (4o). Product is not stable on silica column. Product yield was determined in situ via integration of reactant and product signals versus the internal standard. Yield: 50%. 1 H NMR (CDCl 3, 400 MHz): δ (m, 7H, Ph), 7.09 (d, 2H, J H-H = 7.9 Hz, Ph), 6.96 (t, 1H, J H-H = 7.3 Hz, Ph), 4.73 (s, 2H, CH 2 ), 1.17 (t, 9H, J H-H = 8.1 Hz, - S8 -

9 SiCH 2 CH 3 ), 0.99 (q, 6H, J H-H = 7.2 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 297 [M] +, 268 [M Et] +. 4-methyl-N-(4-methylbenzyl)-N-(triethylsilyl)benzenesulfonamide (4p). Pale yellow oil. Yield: 276 mg (74%, mmol). 1 H NMR (CDCl 3, 400 MHz): δ 7.68 (d, 2H, J H-H = 8.3 Hz, Ph), 7.20 (d, 2H, J H-H = 8.0 Hz, Ph), 7.08 (d, 2H, J H-H = 8.1 Hz, Ph), 7.01 (d, 2H, J H-H = 8.0 Hz, Ph), 4.33 (s, 2H, CH 2 ), 2.39 (s, 3H, CH 3 ), 2.29 (s, 3H, CH 3 ), 0.95 (t, 9H, J H-H = 7.5 Hz, SiCH 2 CH 3 ), 0.84 (q, 6H, J H-H = 7.6 Hz, SiCH 2 CH 3 ). GC (Retention time): min. MS (EI, +ve): m/z 360 [M Et] +. - S9 -

10 1 H NMR Compound 4a C 6 Me 6 - S10 -

11 1 H NMR Compound 4b + Unidentified Product (UP) C 6 Me 6 UP UP UP UP - S11 -

12 1 H NMR Compound 4c C 6 Me 6 - S12 -

13 1 H NMR Compound 4d C 6 Me 6 - S13 -

14 1 H NMR Compound 4e C 6 Me 6 - S14 -

15 1 H NMR Compound 4f C 6 Me 6 - S15 -

16 1 H NMR Compound 4g C 6 Me 6 - S16 -

17 1 H NMR Compound 4h C 6 Me 6 - S17 -

18 1 H NMR Compound 4i C 6 Me 6 - S18 -

19 1 H NMR Compound 4j C 6 Me 6 - S19 -

20 1 H NMR Compound 4k C 6 Me 6 - S20 -

21 1 H NMR Compound 4l C 6 Me 6 - S21 -

22 1 H NMR Compound 4m C 6 Me 6 - S22 -

23 1 H NMR Compound 4n Z Z E C 6 Me 6 Z Z Z E E E E - S23 -

24 1 H NMR Compound 4o B + HSiEt 3 A B B B A A A A B B B HSiEt 3 C 6 Me 6 HSiEt 3 - S24 -

25 1 H NMR Compound 4p C 6 Me 6 (TMS) 2 O HSiEt 3 - S25 -

26 III. Variable Temperature 1 H NMR Investigations Tp* Si-CH 2 -CH 3 Tp* Si-CH 2 -CH 3 Si-H B-Me Al-Me 55 C 45 C 35 C 25 C 55 C 45 C 35 C 25 C Figure S1. Variable temperature 1 H NMR spectra of 2 in the presence of HSiEt 3. - S26 -

27 Tp* Ph Ph CDCl 3 Tp* PhC(O)CH 3 B-Me Al-Me 55 C 45 C 35 C 25 C Figure S2. Variable temperature 1 H NMR spectra of 2 in the presence of acetophenone. - S27 -

28 IV. Deuterium Labeling Studies HSiEt 3 DSiEt 3 D 2 SiPh 2 HDSiPh 2 C 6 Me 6 H 2 SiPh 2 HDSiPh 2 H 2 SiPh 2 HSiEt min 80 min 60 min 50 min 40 min 30 min 20 min 10 min Figure S3. Stack-plot of the 1 H NMR spectra monitoring the H/D exchange between H 2 SiPh 2 and DSiEt 3 in the presence of 2. - S28 -

29 V. X-ray Crystallography Crystallographic Analysis. X-ray structural determinations were performed at the CHEXRAY X-ray diffraction laboratory at the University of California, Berkeley. Single crystals of 1 and 3 were coated in Paratone-N oil, mounted on a Kaptan loop, transferred to a Bruker APEX-I CCD area detector instrument, centered in the beam, and cooled by a nitrogen flow low-temperature apparatus that was previously calibrated by a thermocouple placed at the same position as the crystal. Preliminary orientation matrices and cell constants were determined by collection of second frames followed by spot integration and least-squares refinement. An arbitrary hemisphere of data was collected and the raw data were integrated using SAINT. Cell dimensions reported were calculated from all reflections with I > 10σ. The data were corrected for Lorentz and polarization effects, but no correction for crystal decay was applied. Data were analyzed for agreement and possible absorption using XPREP. An empirical absorption correction based on S3 comparison of redundant and equivalent reflections was applied using SADABS. 6 The structures were solved using SHELXS and refined on all data by full-matrix least squares with SHELXL Thermal parameters for all non-hydrogen atoms were refined anisotropically. Hydrogen atoms were calculated in ideal positions and were riding on their respective carbon atoms. For compound 1, a total of 158 parameters were refined in the final cycle of refinement using 1951 reflections with I > 2σ(I) to yield R 1 and wr 2 of 4.88% and 12.88%, respectively. For compound 3, a total of 310 parameters were refined in the final cycle of refinement using 4341 reflections with I > 2σ(I) to yield R 1 and wr 2 of 2.52% and 4.82%, respectively. Refinement was done using F 2. ORTEP diagrams were created using the ORTEP- 3 software package and rendered using Pov-Ray S29 -

30 Figure S4. ORTEP representation of the asymmetric unit of 1 (including the co-crystallized diethyl ether molecule). - S30 -

31 Table S1. Crystal data and structure refinement for 1. Identification code jk-ii-173 Empirical formula C H 19 Al 0.50 B 0.50 N 3 O 0.50 Formula weight Temperature Wavelength Crystal system Space group 173(2) K Å Monoclinic C2/m Unit cell dimensions a = (3) Å α = 90. b = (3) Å β = (3). c = (2) Å γ = 90. Volume (9) Å 3 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 928 Crystal size 0.29 x 0.07 x 0.07 mm 3 Theta range for data collection 1.81 to Index ranges Reflections collected <=h<=19, -16<=k<=15, -13<=l<=14 Independent reflections 2389 [R(int) = ] Completeness to theta = % Absorption correction SADABS Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2389 / 0 / 158 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = [1951] R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 - S31 -

32 Table S2. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 1. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Al1 2419(1) (1) 33(1) O (2) 0 59(1) N1 1844(1) 1066(1) 5598(1) 30(1) N2 1233(1) 945(1) 4553(1) 31(1) N3 2681(2) (2) 31(1) N4 1847(1) (2) 30(1) B1 1154(2) (3) 31(1) C1 2430(2) 2413(2) 7004(2) 44(1) C2 1850(1) 2029(2) 5898(2) 35(1) C3 1252(2) 2530(2) 5050(2) 41(1) C4 875(1) 1837(2) 4217(2) 37(1) C5 197(2) 1982(2) 3104(2) 53(1) C6 4072(2) (3) 49(1) C7 3125(2) (3) 35(1) C8 2598(2) (3) 40(1) C9 1791(2) (3) 37(1) C10 974(2) 0 992(3) 53(1) C (2) (3) 41(1) C (2) (2) 29(1) C13-688(2) 3403(2) 140(3) 71(1) C (2) 2731(3) 261(3) 78(1) Table S3. Bond lengths [Å] and angles [ ] for 1. Al1-N1# (17) Al1-N (17) Al1-C (3) Al1-C (3) - S32 -

33 O1-C13# (3) O1-C (3) N1-C (3) N1-N (2) N2-C (3) N2-B (2) N3-C (4) N3-N (3) N4-C (4) N4-B (4) B1-N2# (2) C1-C (3) C2-C (3) C3-C (3) C4-C (3) C6-C (4) C7-C (4) C8-C (4) C9-C (4) C13-C (4) N1#1-Al1-N (10) N1#1-Al1-C (8) N1-Al1-C (8) N1#1-Al1-C (8) N1-Al1-C (8) C11-Al1-C (14) C13#2-O1-C (3) C2-N1-N (16) C2-N1-Al (14) N2-N1-Al (12) C4-N2-N (16) C4-N2-B (18) N1-N2-B (17) C7-N3-N (2) C9-N4-N (2) - S33 -

34 C9-N4-B (2) N3-N4-B (2) N4-B1-N (16) N4-B1-N2# (16) N2-B1-N2# (2) N1-C2-C (19) N1-C2-C (19) C3-C2-C (2) C4-C3-C (19) N2-C4-C (19) N2-C4-C (2) C3-C4-C (2) N3-C7-C (3) N3-C7-C (3) C8-C7-C (3) C9-C8-C (3) N4-C9-C (3) N4-C9-C (3) C8-C9-C (3) O1-C13-C (3) Symmetry transformations used to generate equivalent atoms: #1 x,-y,z #2 -x,y,-z Table S4. Anisotropic displacement parameters (Å 2 x 10 3 ) for 1. The anisotropic displacement factor exponent takes the form: -2p 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Al1 36(1) 27(1) 32(1) 0 3(1) 0 O1 53(2) 70(2) 55(2) 0 17(1) 0 N1 34(1) 27(1) 29(1) -1(1) 7(1) -1(1) N2 32(1) 29(1) 30(1) 0(1) 6(1) 4(1) N3 34(1) 26(1) 32(1) 0 6(1) 0 N4 34(1) 29(1) 26(1) 0 3(1) 0 B1 30(2) 33(2) 29(2) 0 2(1) 0 - S34 -

35 C1 61(1) 31(1) 43(1) -8(1) 16(1) -5(1) C2 46(1) 27(1) 34(1) -1(1) 17(1) -1(1) C3 61(1) 27(1) 40(1) 3(1) 21(1) 10(1) C4 44(1) 34(1) 36(1) 7(1) 14(1) 12(1) C5 60(2) 50(2) 44(1) 7(1) 6(1) 24(1) C6 42(2) 48(2) 61(2) 0 22(2) 0 C7 41(2) 24(1) 41(2) 0 14(1) 0 C8 55(2) 36(2) 32(2) 0 19(2) 0 C9 51(2) 32(2) 26(2) 0 7(1) 0 C10 61(2) 62(2) 30(2) 0 1(2) 0 C11 38(2) 41(2) 39(2) 0 1(1) 0 C12 47(2) 23(1) 20(1) 0 12(1) 0 C13 74(2) 78(2) 62(2) 5(2) 23(2) 18(2) C14 53(2) 119(3) 63(2) 14(2) 16(2) 15(2) Table S5. Hydrogen coordinates (x 10 4 ) and isotropic displacement parameters (Å 2 x10 3 ) for 1. x y z U(eq) H1 556(18) (30) 28(7) H1A H1B H1C H3A H5A H5B H5C H6A H6B H6C H6D H6E H6F H8A S35 -

36 H10A H10B H10C H10D H10E H10F H11A H11B H11C H11D H11E H11F H12A H12B H12C H12D H12E H12F H13A H13B H14A H14B H14C S36 -

37 Figure S5. ORTEP representation of the asymmetric unit of 3 (including the triiodide counterion and the co-crystallized methylene chloride molecule). - S37 -

38 Table S6. Crystal data and structure refinement for 3. Identification code jk-iii-23 Empirical formula C 17 H 27 Al B Cl 2 I 3 N 6 Formula weight Temperature Wavelength Crystal system 133(2) K Å Space group P2 1 /c Monoclinic Unit cell dimensions a = (3) Å α = 90. b = (15) Å β = (2). c = (2) Å γ = 90. Volume (7) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1528 Crystal size 0.17 x 0.12 x 0.10 mm 3 Theta range for data collection 1.21 to Index ranges Reflections collected <=h<=20, -13<=k<=13, -17<=l<=15 Independent reflections 5061 [R(int) = ] Completeness to theta = % Absorption correction SADABS Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5061 / 0 / 310 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = [4341] R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 - S38 -

39 Table S7. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 3. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) Al1-3383(1) 600(1) -2735(1) 25(1) B1-1657(2) 667(3) -1675(2) 24(1) I1 1377(2) 3273(3) 2123(2) 42(1) I2 3113(2) 3208(3) 3053(3) 33(1) I3 4817(2) 3177(3) 4012(2) 40(1) I1' 1258(7) 3379(8) 2004(8) 61(2) I2' 3011(7) 3201(6) 2956(8) 47(1) I3' 4744(5) 3128(6) 3934(6) 62(2) Cl1-1291(1) 3048(1) -3665(1) 70(1) Cl2-3000(1) 3074(1) -4710(1) 78(1) N1-2861(1) 2030(2) -2173(2) 27(1) N2-2045(1) 1920(2) -1693(2) 27(1) N3-2888(1) -308(2) -1575(2) 27(1) N4-2067(1) -202(2) -1184(2) 27(1) N5-2659(1) 184(2) -3354(2) 26(1) N6-1865(1) 263(2) -2753(2) 27(1) C1-3896(2) 3578(3) -2524(3) 38(1) C2-3058(2) 3162(3) -2075(2) 30(1) C3-2373(2) 3781(3) -1538(2) 32(1) C4-1754(2) 2981(3) -1311(2) 30(1) C5-887(2) 3188(3) -772(3) 43(1) C6-3946(2) -1386(3) -1232(3) 38(1) C7-3098(2) -1088(3) -1020(2) 30(1) C8-2412(2) -1502(3) -285(2) 34(1) C9-1781(2) -930(3) -406(2) 30(1) C10-914(2) -1041(3) 180(2) 42(1) C (2) -409(3) -5059(2) 39(1) C (2) -227(3) -4231(2) 30(1) C (2) -410(3) -4189(2) 34(1) C (2) -92(3) -3251(2) 31(1) C15-528(2) -125(3) -2809(3) 43(1) - S39 -

40 C (2) 576(3) -3445(2) 37(1) C (3) 3797(4) -3874(3) 56(1) Table S8. Bond lengths [Å] and angles [ ] for 3. Al1-N (3) Al1-N (3) Al1-N (3) Al1-C (3) B1-N (4) B1-N (4) B1-N (4) B1-H1 1.10(3) I1-I (5) I2-I (5) I1'-I2' 2.972(11) I2'-I3' 2.935(10) Cl1-C (4) Cl2-C (4) N1-C (4) N1-N (3) N2-C (4) N3-C (4) N3-N (3) N4-C (4) N5-C (4) N5-N (3) N6-C (4) C1-C (4) C1-H1A C1-H1B C1-H1C C2-C (4) - S40 -

41 C3-C (4) C3-H3A C4-C (4) C5-H5A C5-H5B C5-H5C C6-C (4) C6-H6A C6-H6B C6-H6C C7-C (4) C8-C (4) C8-H8A C9-C (4) C10-H10A C10-H10B C10-H10C C11-C (4) C11-H11A C11-H11B C11-H11C C12-C (4) C13-C (4) C13-H13A C14-C (4) C15-H15A C15-H15B C15-H15C C16-H16A C16-H16B C16-H16C C17-H17A C17-H17B N1-Al1-N (11) N1-Al1-N (11) - S41 -

42 N5-Al1-N (11) N1-Al1-C (13) N5-Al1-C (13) N3-Al1-C (13) N6-B1-N (2) N6-B1-N (2) N4-B1-N (2) N6-B1-H (15) N4-B1-H (15) N2-B1-H (15) I3-I2-I (15) I3'-I2'-I1' 177.5(3) C2-N1-N (2) C2-N1-Al (2) N2-N1-Al (18) C4-N2-N (2) C4-N2-B (2) N1-N2-B (2) C7-N3-N (2) C7-N3-Al (2) N4-N3-Al (18) C9-N4-N (2) C9-N4-B (3) N3-N4-B (2) C12-N5-N (2) C12-N5-Al (2) N6-N5-Al (18) C14-N6-N (2) C14-N6-B (3) N5-N6-B (2) C2-C1-H1A C2-C1-H1B H1A-C1-H1B C2-C1-H1C H1A-C1-H1C H1B-C1-H1C S42 -

43 N1-C2-C (3) N1-C2-C (3) C3-C2-C (3) C4-C3-C (3) C4-C3-H3A C2-C3-H3A N2-C4-C (3) N2-C4-C (3) C3-C4-C (3) C4-C5-H5A C4-C5-H5B H5A-C5-H5B C4-C5-H5C H5A-C5-H5C H5B-C5-H5C C7-C6-H6A C7-C6-H6B H6A-C6-H6B C7-C6-H6C H6A-C6-H6C H6B-C6-H6C N3-C7-C (3) N3-C7-C (3) C8-C7-C (3) C9-C8-C (3) C9-C8-H8A C7-C8-H8A N4-C9-C (3) N4-C9-C (3) C8-C9-C (3) C9-C10-H10A C9-C10-H10B H10A-C10-H10B C9-C10-H10C H10A-C10-H10C H10B-C10-H10C S43 -

44 C12-C11-H11A C12-C11-H11B H11A-C11-H11B C12-C11-H11C H11A-C11-H11C H11B-C11-H11C N5-C12-C (3) N5-C12-C (3) C13-C12-C (3) C14-C13-C (3) C14-C13-H13A C12-C13-H13A N6-C14-C (3) N6-C14-C (3) C13-C14-C (3) C14-C15-H15A C14-C15-H15B H15A-C15-H15B C14-C15-H15C H15A-C15-H15C H15B-C15-H15C Al1-C16-H16A Al1-C16-H16B H16A-C16-H16B Al1-C16-H16C H16A-C16-H16C H16B-C16-H16C Cl2-C17-Cl (2) Cl2-C17-H17A Cl1-C17-H17A Cl2-C17-H17B Cl1-C17-H17B H17A-C17-H17B S44 -

45 Table S9. Anisotropic displacement parameters (Å 2 x 10 3 ) for 3. The anisotropic displacement factor exponent takes the form: -2p 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 Al1 21(1) 26(1) 26(1) 2(1) 5(1) 0(1) B1 18(2) 27(2) 22(2) -1(1) 3(1) -3(1) I1 40(1) 34(1) 51(1) -3(1) 17(1) 2(1) I2 42(1) 26(1) 35(1) 1(1) 19(1) 0(1) I3 42(1) 44(1) 40(1) 0(1) 20(1) 0(1) I1' 51(2) 43(1) 93(3) -3(2) 33(2) 7(1) I2' 68(3) 28(1) 59(3) -3(1) 39(2) 8(1) I3' 81(3) 48(2) 62(2) 4(1) 30(2) 14(2) Cl1 72(1) 63(1) 77(1) -1(1) 29(1) 1(1) Cl2 82(1) 84(1) 55(1) -1(1) 7(1) -5(1) N1 22(1) 30(1) 28(1) 1(1) 7(1) 1(1) N2 21(1) 27(1) 29(1) -1(1) 6(1) -2(1) N3 24(1) 26(1) 29(1) 2(1) 8(1) 2(1) N4 21(1) 30(1) 26(1) 0(1) 4(1) 3(1) N5 22(1) 29(1) 25(1) 0(1) 4(1) -2(1) N6 20(1) 29(1) 29(1) 1(1) 6(1) -1(1) C1 35(2) 32(2) 47(2) 3(2) 16(2) 4(1) C2 32(2) 28(2) 31(2) 3(1) 14(1) 0(1) C3 39(2) 26(2) 32(2) -3(1) 13(2) -3(1) C4 31(2) 32(2) 26(2) -1(1) 8(1) -7(1) C5 37(2) 40(2) 43(2) -7(2) 5(2) -10(2) C6 41(2) 36(2) 41(2) 3(2) 20(2) -4(2) C7 39(2) 26(2) 29(2) -1(1) 17(2) -1(1) C8 44(2) 31(2) 25(2) 5(1) 11(2) 5(2) C9 34(2) 31(2) 25(2) 1(1) 8(1) 7(1) C10 37(2) 47(2) 34(2) 8(2) 3(2) 8(2) C11 40(2) 45(2) 28(2) -4(2) 6(2) -9(2) C12 34(2) 28(2) 26(2) 1(1) 8(1) -3(1) C13 38(2) 36(2) 31(2) -3(1) 17(2) -4(2) C14 29(2) 32(2) 33(2) 2(1) 12(1) 0(1) C15 28(2) 56(2) 47(2) -4(2) 16(2) 2(2) - S45 -

46 C16 27(2) 41(2) 40(2) 1(2) 8(2) -3(1) C17 74(3) 48(2) 56(3) -1(2) 35(2) -7(2) Table S10. Hydrogen coordinates (x10 4 ) and isotropic displacement parameters (Å 2 x10 3 ) for 3. x y z U(eq) H1-1012(18) 710(30) -1290(20) 28(8) H1A H1B H1C H3A H5A H5B H5C H6A H6B H6C H8A H10A H10B H10C H11A H11B H11C H13A H15A H15B H15C H16A H16B H16C H17A H17B S46 -

47 VI. References (1) Wu, X.-F.; Vovard-Le Bray, C.; Bechki, L.; Darcel, C. Tetrahedron 2009, 65, (2) Caseri, W.; Pregosin, P. S. J. Organomet. Chem. 1988, 356, (3) Han, R.; Looney, A.; Parkin, G. J. Am. Chem. Soc. 1989, 111, (4) Looney, A.; Parkin, G. Polyhedron 1990, 9, (5) Wernerova, M.; Hudlicky, T. Synlett 2010, 18, (6) SADABS; Bruker-AXS Madison, WI, (7) SHELXTL6; Bruker-AXS Madison, WI, S47 -