Supporting Information
|
|
- Brittany Mills
- 5 years ago
- Views:
Transcription
1 Thomas Özgün, Guo-Qiang Chen, Constantin G. Daniliuc, Alison C. McQuilken, Timothy H. Warren, Robert Knitsch, Hellmut Eckert, Gerald Kehr, Gerhard Erker* Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Corrensstrasse 40, Münster, Germany Department of Chemistry, Georgetown University, Box , Washington, D.C , United States Institut für Physikalische Chemie, Westfälische Wilhelms-Universität, Corrensstrasse 30, Münster, Germany Supporting Information S1
2 Table of contents 1 General Procedures Experimental Part Synthesis of compounds... 5 Synthesis of compound Synthesis of compound 10a... 7 Synthesis of compound 10b Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of compound Generation of compound 14-D Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of compound Synthesis of compound Solid State NMR Data EPR Data S2
3 1 General Procedures All syntheses involving air- and moisture sensitive compounds were carried out using standard Schlenk-type glassware (or in a glove box) under an atmosphere of argon. Solvents were dried and stored under an argon atmosphere. NMR spectra were recorded on an Agilent DD2-500 MHz ( 1 H: 500 MHz, 13 C: 126 MHz, 19 F: 470 MHz, 11 B: 160 MHz, 31 P: 202 MHz) and on an Agilent DD2-600 MHz ( 1 H: 600 MHz, 13 C: 151 MHz, 19 F: 564 MHz, 11 B: 192 MHz, 31 P: 243 MHz). 1 H NMR and 13 C NMR: chemical shifts are given relative to TMS and referenced to the solvent signal. 19 F NMR: chemical shifts are given relative to CFCl 3 (δ = 0, external reference), 11 B NMR: chemical shifts are given relative to BF 3 Et 2O (δ = 0, external reference), 31 P NMR: chemical shifts are given relative to H 3PO 4 (85% in D 2O) (δ = 0, external reference). NMR assignments were supported by additional 2D NMR experiments. Elemental analyses were performed on an Elementar Vario El III. IR spectra were recorded on a Varian 3100 FT-IR (Excalibur Series). Melting points and decomposition points were obtained with a DSC 2010 (TA Instruments). HRMS was recorded on GTC Waters Micromass (Manchester, UK). X-Ray diffraction: For compounds 10a, 10b, 12, 14, 19, 21 and 22 data sets were collected with a Nonius Kappa CCD diffractometer. Programs used: data collection, COLLECT (R. W. W. Hooft, Bruker AXS, 2008, Delft, The Netherlands); data reduction Denzo-SMN (Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, ); absorption correction, Denzo (Z. Otwinowski, D. Borek, W. Majewski, W. Minor, Acta Crystallogr. 2003, A59, ); structure solution SHELXS-97 (G. M. Sheldrick, Acta Crystallogr. 1990, A46, ); structure refinement SHELXL-97 (G. M. Sheldrick, Acta Crystallogr. 2008, A64, ) and graphics, XP (BrukerAXS, 2000). For compound 18 and 20 data sets were collected with a Kappa CCD APEXII Bruker diffractometer. For compounds 11, 17, 20 data sets were collected with a D8 Venture Dual Source 100 CMOS diffractometer. Programs used: data collection: APEX2 V (Bruker AXS Inc., 2014); cell refinement: SAINT V8.34A (Bruker AXS Inc., 2013); data reduction: SAINT V8.34A (Bruker AXS Inc., 2013); absorption correction, SADABS V2014/2 (Bruker AXS Inc., 2014); structure solution SHELXT-2014 (Sheldrick, 2014); structure refinement SHELXL-2014 (Sheldrick, 2014) and graphics, XP (Bruker AXS Inc., 2014). R- values are given for observed reflections, and wr 2 values are given for all reflections. Exceptions and special features: For compound 11 one pentane molecule, for compound 14 one dichloromethane molecule, for compounds 19 and 20 two dichloromethane molecules and for compound 21 one phenyl group and one part of the six membered ring C5 to C10 are disordered over two positions. Several restraints (SADI, SAME, ISOR and SIMU) were used in order to improve refinement stability. For compounds 10a and 12 one badly pentane molecule and for compounds 17 and 18 one badly half pentane molecule were found in the asymmetric unit and could not be satisfactorily refined. The program SQUEEZE (A. L. Spek J. S3
4 Appl. Cryst., 2003, 36, 7-13) was therefore used to remove mathematically the effect of the solvent. The quoted formula and derived parameters are not included the squeezed solvent molecules. Compound 10b presents one tbu group and one six membered ring at C1 atom disordered over two positions. Several restraints (SADI, SAME, ISOR and SIMU) were used in order to improve refinement stability. Moreover, one badly disordered pentane molecule was found in the asymmetrical unit and could not be satisfactorily refined. The program SQUEEZE was therefore used to remove mathematically the effect of the solvent. The quoted formula and derived parameters are not included the squeezed solvent molecule. Materials: Vinylboranes 6a, 6b [Ekkert, O.; Tuschewitzki, O.; Daniliuc, C. G.; Kehr, G.; Erker, G. Chem. Commun., 2013, 49, ; Parks, D. J.; Piers, W. E.; Yap, G. P. A. Organometallics, 1998, 17, ] were prepared according to the literature. S4
5 2 Experimental Part 2.1 Synthesis of compounds Synthesis of compound 9 For analogous synthesis of the diphenylphospane derivative see: Chen, G.-Q.; Kehr, G.; Daniliuc, C. G.; Erker, G. Org. Biomol. Chem. 2015, 13, Scheme S1 n-butyllithium (10.0 ml, 16.0 mmol, 1.0 eq) was added dropwise to a solution of 1- ethynylcyclohexene (1.9 ml, 1.7 g, 16.0 mmol, 1.0 eq) in tetrahydrofuran (80 ml) at -78 C. The reaction mixture was warmed to r. t. and stirred for 10 min. Then a solution of chlorodimesitylphosphane (4.9 g, 16.0 mmol, 1.0 eq) in tetrahydrofuran (30 ml) was added dropwise to the obtained dark brown suspension at -78 C. The reaction mixture was stirred for 10 min at -78 C and subsequently stirred for 2 hours at ambient temperature. Then all volatiles were removed in vacuo and the sticky residue was suspended in pentane (100 ml). The resulting suspension was filtered via cannula (WHATMAN glass fiber filter) and all volatiles were removed from the filtrate in vacuo to give a brown oil. After Purification via column chromatography (silica: CH 2Cl 2:CyH = 15:85; R f: 0.70) compound 9 was obtained as a colorless, crystalline solid (5.1 g, 13.6 mmol, 85%). IR (KBr): ṽ [cm -1 ] = 3063 (w), 2958 (w), 2855 (w), 2727 (w), 2661 (w), 2466 (w), 2300 (w), 2133 (m), 1908 (w), 1881 (w), 1720 (w), 1601 (m), 1553 (w), 1465 (m), 1433 (s), 1407 (m), 1372 (m), 1346 (w), 1074 (w), 1028 (m), 996 (w), 917 (m), 845 (s), 787 (m), 712 (w), 689 (m), 616 (m), 600 (m), 558 (s), 460 (w), 431 (w). M.p. 80 C. Anal. Calc. for C 26H 31P: C: 83.39; H: Found: C: 83.20; H: H NMR (500 MHz, dichloromethane-d 2, 299 K): δ 6.81 (dm, 4 J PH = 3.2 Hz, 4H, m-mes), 6.08 (m, 1H, 2-CH), 2.37 (s, 12H, o-mes), 2.24 (s, 6H, p-mes), 2.11 (m, 2H, 6-CH 2), 2.09 (m, 2H, 3- CH 2), 1.62 (m, 2H, 5-CH 2), 1.57 (m, 2H, 4-CH 2). 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 299 K): δ (d, 2 J PC = 15.6 Hz, o-mes), (p-mes), (d, 4 J PC = 2.6 Hz, 2-CH), (d, 1 J PC = 12.6 Hz, i-mes), (d, 3 J PC = 3.6 Hz, m-mes), (d, 3 J PC = 1.5 Hz, 1-C=), (d, 2 J PC = 8.8 Hz, C), 84.3 (d, 1 J PC = 3.4 Hz, PC ), 28.8 (d, 4 J PC = 1.6 Hz, 6-CH 2), 26.1 (3-CH 2), 23.0 (d, 3 Mes J PC = 14.4 Hz, o-ch 3 ), 22.6 (5-CH 2), 21.8 (4-CH 2), Mes 21.0 (p-ch 3 ). S5
6 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 299 K): δ ( 1/2 ~ 3 Hz). Figure S1: 1 H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of compound 9 Figure S2: 13 C{ 1 H} NMR (126 MHz, dichloromethane-d2, 299 K) spectrum of compound 9 S6
7 Figure S3: 31 P{ 1 H} NMR (202 MHz, dichloromethane-d2, 299 K) spectrum of compound 9 Synthesis of compound 10a Scheme S2 A solution of phosphane 9 (417.6 mg, 1.1 mmol, 1.0 eq) in toluene (6 ml) was added to a solution of borane 6a (500.0 mg, 1.1 mmol, 1.0 eq) in toluene (4 ml). The reaction mixture was stirred at 60 C for 3 d and then all volatiles were removed in vacuo. The resulting sticky residue was dissolved in pentane (3 ml), which was subsequently removed in vacuo. The obtained solid was washed with pentane (5 x 3 ml) to give compound 10a as a white powdery solid (822.0 mg, 1.0 mmol, 90%). IR (KBr): ṽ [cm -1 ] = 3696 (w), 3023 (m), 2929 (s), 2856 (m), 2347 (w), 1947 (w), 1723 (w), 1642 (s), 1604 (s), 1553 (w), 1515 (s), 1455 (m), 1380 (m), 1341 (w), 1287 (s), 1269 (m), 1248 (m), 1152 (w), 1091 (s), 1034 (m), 1024 (w), 996 (s), 852 (s), 805 (m), 773 (m), 741 (s), 696 (s), 643 (m), 629 (m), 607 (m), 575 (m), 553 (m), 499 (m), 453 (w), 418 (m). Decomp. 200 C. Anal. Calc. for C 46H 38BF 10P: C: 67.17; H: Found: C: 66.78; H: H NMR (600 MHz, dichloromethane-d 2, 213 K): δ 7.28 (m, 2H, o-ph), 7.23 (m, 2H, m-ph), 7.18 (m, 1H, p-ph), 7.14 (br d, 3 J HH = 16.3 Hz, 1H, =CH), 6.97 (d, 4 J PH = 3.5 Hz, 1H, m- Mes a ), 6.81 (s, 1H, m -Mes a ), 6.79 (m, 1H, m-mes b ), 6.40 (d, 3 J HH = 16.3 Hz, 1H, =CH Ph ), 6.38 (d, 4 J PH = 2.5 Hz, 1H, m -Mes b Mes,b ), 5.87 (s, 1H, 2-CH), 2.57 (s, 3H, o-ch 3 ), 2.45 (m, 3H, o- Mes,a CH 3 ), 2.30, 2.20 (each m, each 1H, 3-CH 2) t Mes,a, 2.23 (s, 3H, p-ch 3 ), 2.20 (s, 3H, o - S7
8 Mes,a Mes,b CH 3 ), 2.10 (s, 3H, p-ch 3 ), 1.77, 1.70 (each m, each 1H, 5-CH 2) t, 1.65, 1.52 (each m, each 1H, 4-CH 2) t Mes,b, 1.61 (s, 3H, o -CH 3 ), 1.58, 1.43 (each m, each 1H, 6-CH 2) t. [ t tentatively assigned] 13 C{ 1 H} NMR (151 MHz, dichloromethane-d 2, 213 K): δ (d, 2 J PC = 29.6 Hz, BC=), (d, 2 J PC = 17.8 Hz, o-mes a ), (o -Mes a ), (d, 2 J PC = 3.4 Hz, o-mes b ), (d, 4 J PC = 2.4 Hz, p-mes a ), (p-mes b ), (d, 2 J PC = 10.2 Hz, o -Mes b ), (d, 1 J PC = 50.6 Hz, PC=), (=CH Ph ), (i-ph), (d, 2 J PC = 3.3 Hz, 1-C=), (d, 3 J PC = 8.3 Hz, m- Mes b ), (d, 3 J PC = 8.3 Hz, 2-CH), (d, 3 J PC = 5.9 Hz, m -Mes a ), (d, 3 J PC = 9.2 Hz, m-mes a ), (d, 3 J PC = 9.2 Hz, m -Mes b ), (m-ph), (p-ph), (o-ph), (d, 1 J PC = 25.3 Hz, i-mes a ), (d, 1 J PC = 39.9 Hz, i-mes b ), (d, 3 J PC = 46.8 Hz, =CH), 27.4 (5-CH 2) t, 25.3 (3-CH 2) t, 25.0 (br d, 3 Mes,b J PC = 13.5 Hz, o-ch 3 ), 23.7 (dm, J = 8.7 Hz, o- Mes,a CH 3 ), 22.4 (6-CH 2) t, 22.3 (d, 3 Mes,a J PC = 2.2 Hz, o -CH 3 ), 22.0 (dd, J = 9.5 Hz, J = 3.9 Hz, Mes,b o -CH 3 ), 21.5 (4-CH 2) t Mes,a Mes,b, 20.7 (p-ch 3 ), 20.1 (p-ch 3 ). [C 6F 5 not listed; t tentatively assigned] 31 P{ 1 H} NMR (243 MHz, dichloromethane-d 2, 213 K): δ 8.8 (partial relaxed 1:1:1:1 q, J PB ~ 25 Hz). 11 B{ 1 H} NMR (192 MHz, dichloromethane-d 2, 213 K): δ 2.0 ( 1/2 ~ 1900 Hz) 19 F NMR (564 MHz, dichloromethane-d 2, 213 K): δ (m, o), (m, o ), (t, 3 J FF = 21.3 Hz, p), (m, m ), (m, m)(each 1F, C 6F 5)[ 19 F mp = 5.8, 6.6], (o), (o ), (m, p), (m, m ), (m, m)(each 1F, C 6F 5)[ 19 F mp = 6.2, 6.5]. Figure S4: 1 H NMR (600 MHz, dichloromethane-d2, 213 K) spectrum of compound 10a S8
9 Figure S5: 13 C{ 1 H} NMR (151 MHz, dichloromethane-d2, 213 K) spectrum of compound 10a Figure S6: 11 B{ 1 H} NMR (192 MHz, dichloromethane-d2, 213 K) and 31 P{ 1 H} NMR (243 MHz, dichloromethaned2, 213 K) spectra of compound 10a S9
10 Figure S7: 19 F NMR (564 MHz, dichloromethane-d2, 213 K) spectrum of compound 10a Figure S8: Dynamic 1 H NMR (600 MHz, dichloromethane-d2) spectra of compound 10a S10
11 Figure S9: Dynamic 19 F NMR (564 MHz, dichloromethane-d2) spectra of compound 10a G [T c, (T)] = RT c( ln(tc/ )) [J/mol] T c = coalescence temperature [K]: 286 K ( 19 F, p-bc 6F 5) = chemical shift difference [Hz] ( 19 F, p-bc 6F 5, 233 K): 883 Hz R = J/(mol K); 1 J = cal G [286 K, (233 K) = 883 Hz] = J/mol = 12.4 ± 0.3 kcal/mol Crystals suitable for the X-ray crystal structure analysis were obtained from a dichloromethane solution of compound 10a at -35 C: X-ray crystal structure analysis of compound 10a: formula C 46H 38BF 10P, M = , colourless crystal, 0.15 x 0.10 x 0.06 mm, a = (2), b = (2), c = (3) Å, α = (1), β = (1), γ = (1), V = (1) Å 3, ρ calc = gcm -3, μ = mm -1, empirical absorption correction (0.981 T 0.992), Z = 2, triclinic, space group P1 (No. 2), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), 7974 independent (R int = 0.047) and 6146 observed reflections [I>2σ(I)], 529 refined parameters, R = 0.070, wr 2 = 0.191, max. (min.) residual electron density 0.31 (-0.31) e.å -3, hydrogen atoms were calculated and refined as riding atoms. S11
12 Figure S10: X-ray crystal structure of compound 10a (thermal ellipsoids are shown at the 30% probability level) Synthesis of compound 10b Scheme S3 A solution of borane 6b (1.54 g, 3.60 mmol, 1.0 eq) in toluene (5 ml) was added dropwise to a solution of phosphane 9 (1.35 g, 3.60 mmol, 1.0 eq) in toluene (5 ml). The reaction mixture was stirred at 60 C for 3 days and then all volatiles were removed in vacuo. The resulting sticky red residue was dissolved in pentane (5 ml), which was subsequently removed in vacuo. The obtained solid was washed with pentane (5 x 3 ml) and dried to finally give compound 10b as an off-white solid (1.26 g, 1.6 mmol, 43%). IR (KBr): ṽ [cm -1 ] = 5340 (w), 4382 (w), 4310 (w), 3901 (w), 3819 (w), 3747 (w), 3673 (w), 3628 (w), 3156 (w), 3026 (s), 2954 (s), 2863 (s), 2739 (w), 2632 (w), 2568 (w), 2400 (w), S12
13 2360 (w), 2220 (w), 2093 (w), 1828 (w), 1772 (w), 1735 (w), 1699 (w), 1645 (s), 1605 (m), 1515 (m), 1445 (m), 1381 (m), 1177 (w), 1114 (s), 1032 (m), 966 (m), 925 (m), 854 (s), 805 (m), 772 (m), 743 (s), 695 (s), 668 (s), 630 (s), 609 (s), 574 (m), 554 (m), 533 (m), 498 (m), 456 (m), 417 (m). Decomp. 212 C. Anal. Calc. for C 44H 42BF 10P: C: 65.85; H: Found: C: 65.79; H: H NMR (500 MHz, dichloromethane-d 2, 213 K): δ 6.95 (d, 4 J PH = 3.0 Hz, 1H, m-mes a ), 6.78 (s, 1H, m -Mes a ), 6.76 (s, 1H, m -Mes b ), 6.34 (s, 1H, m-mes b ), 6.15 (d, 3 J HH = 16.0 Hz, 1H, =CH), 5.72 (s, 1H, 2-CH), 5.62 (d, 3 J HH = 16.0 Hz, 1H, =CH tbu Mes,b ), 2.53 (s, 3H, o -CH 3 ), 2.44 (br, 3H, Mes,a Mes,a o-ch 3 ), 2.21 (s, 3H, p-ch 3 ), 2.18, 2.13 (each m, each 1H, 3-CH 2) t, 2.16 (s, 3H, o - Mes,a Mes,b CH 3 ), 2.09 (s, 3H, p-ch 3 ), 1.71, 1.67 (each br m, each 1H, 5-CH 2) t, 1.59, 1.45 (each m, each 1H, 4-CH 2), Mes,b 1.56 (s, 3H, o-ch 3 ), 1.53, 1.40 (each m, each 1H, 6-CH 2), 0.75 (s, tbu 9H, CH 3 ). [ t tentatively assigned] 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 213 K): δ (br d, 2 J PC = 30 Hz, BC=), (=CH tbu ), (d, 2 J PC = 17.2 Hz, o-mes a ), (o -Mes a ), (d, 2 J PC = 3.4 Hz, o -Mes b ), (d, 4 J PC = 1.7 Hz, p-mes a ), (d, 2 J PC = 13.2 Hz, o-mes b ), (d, 4 J PC = 2.1 Hz, p- Mes b ), (d, 1 J PC = 51.1 Hz, PC=), (d, 2 J PC = 3.5 Hz, 1-C=), (d, 3 J PC = 8.2 Hz, m -Mes b ), (d, 3 J PC = 6.9 Hz, 2-CH), (d, 3 J PC = 6.9 Hz, m -Mes a ), (d, 3 J PC = 9.1 Hz, m-mes a ), (d, 3 J PC = 9.1 Hz, m-mes b ), (d, 1 J PC = 25.0 Hz, i-mes a ), (d, 1 J PC = 39.6 Hz, i-mes b ), (d, 3 J PC = 45.5 Hz, =CH), 33.3 (C tbu tbu ), 28.0 (CH 3 ), 27.4 (5-CH 2) t, 25.2 (3-CH 2) t Mes,b Mes,a, 24.9 (m, o -CH 3 ), 23.6 (m, o-ch 3 ), 22.4 (6-CH 2) t, 22.3 (d, 3 J PC = 2.3 Hz, Mes,a Mes,b o -CH 3 ), 22.0 (dd, J = 9.3 Hz, J = 3.4 Hz, o-ch 3 ), 21.5 (4-CH 2) t Mes,a, 20.7 (p-ch 3 ), 20.0 Mes,b (p-ch 3 ). [C 6F 5 not listed; t tentatively assigned] 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 213 K): δ 10.9 (partial relaxed 1:1:1:1 q J PB ~ 26 Hz). 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 299 K): δ 12.8 ( 1/2 ~ 37 Hz). 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 213 K): δ -3.0 (ν 1/2 ~ 2400 Hz). 19 F NMR (470 MHz, dichloromethane-d 2, 213 K): δ (m, o), (m, o ), (br t, 3 J FF = 21.3 Hz, p), (m, m), (m, m )(each 1F, C 6F 5)[ 19 F m,p = 6.0, 6.2]; (m, o), (m, o ), (br t, 3 J FF = 17.0 Hz, p), (m, m ), (m, m)(each 1F, C 6F 5)[ 19 F m,p = 6.1, 6.3] S13
14 Figure S11: 1 H NMR (500 MHz, dichloromethane-d2, 213 K) spectrum of compound 10b Figure S12: 13 C{ 1 H} NMR (126 MHz, dichloromethane-d2, 213 K) spectrum of compound 10b S14
15 Figure S13: 19 F NMR (470 MHz, dichloromethane-d2, 213 K) spectrum of compound 10b Figure S14: 31 P{ 1 H} NMR (202 MHz, dichloromethane-d2) spectra of compound 10b at 299 K (1) and 213 K (2) Figure S15: 11 B{ 1 H} NMR (160 MHz, dichloromethane-d2) spectra of compound 10b at 299 K (1) and 213 K (2) S15
16 Figure S16: Dynamic 1 H NMR (500 MHz, dichloromethane-d2) spectra of compound 10b Figure S17: Dynamic 19 F NMR (470 MHz, dichloromethane-d2) spectra of compound 10b S16
17 G [T c, (T)] = RT c( ln(tc/ )) [J/mol] T c= coalescence temperature [K]: 286 K ( 19 F, p-bc 6F 5) = chemical shift difference [Hz] ( 19 F, p-bc 6F 5, 233 K): 567 Hz R = J/(mol K); 1 J = cal G [286 K, (233 K) = 567 Hz] = J/mol = 12.7 ± 0.3 kcal/mol Crystals suitable for the X-ray crystal structure analysis were obtained from a solution of 10b in pentane at -35 C: X-ray crystal structure analysis of compound 10b: formula C 44H 42BF 10P, M = , colourless crystal, 0.22 x 0.06 x 0.01 mm, a = (3), b = (3), c = (6) Å, α = (1), β = (1), γ = (2), V = (1) Å 3, ρ calc = gcm -3, μ = mm -1, empirical absorption correction (0.973 T 0.998), Z = 2, triclinic, space group P1 (No. 2), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), 8122 independent (R int = 0.067) and 5633 observed reflections [I>2σ(I)], 603 refined parameters, R = 0.087, wr 2 = 0.233, max. (min.) residual electron density 0.29 (-0.29) e.å -3, hydrogen atoms were calculated and refined as riding atoms. Figure S18: X-ray crystal structure of compound 10b (thermal ellipsoids are shown at the 30% probability level) S17
18 Synthesis of compound 11 Scheme S4 A solution of compound 10a (515.2 mg, mol, 1.0 eq) in toluene (5 ml) was stirred at 80 C for 3 days. Then all volatiles were removed in vacuo and the resulting sticky residue was dissolved in pentane (3 ml), which was subsequently removed in vacuo. After suspending the obtained sticky solid in pentane (3 ml) the precipitate was collected, washed with pentane (3 x 2 ml) and dried in vacuo to give compound 11 as a white solid (454.2 mg, mol, 88%). IR (KBr): ṽ [cm -1 ] = 3696 (w), 3027 (m), 2959 (m), 2934 (s), 2856 (m), 2797 (w), 2295 (w), 1642 (m), 1602 (s), 1556 (w), 1515 (s), 1460 (s), 1384 (m), 1283 (m), 1246 (m), 1204 (w), 1094 (s), 1040 (w), 1011 (w), 968 (s), 907 (w), 853 (s), 834 (w), 769 (m), 739 (s), 702 (s), 675 (m), 640 (m), 597 (w), 555 (s), 534 (w), 510 (w), 482 (w), 427 (m). M.p. 130 C. Anal. Calc. for C 46H 38BF 10P: C: 67.17; H: Found: C: 66.79; H: A solution of the white solid in dichloromethane-d 2 showed at 213 K a mixture of two isomers 11 and 11 [ratio ca. 77 : 23 ( 31 P)]. Major component (11): 1 H NMR (500 MHz, dichloromethane-d 2, 213 K): δ 7.29 (m, 2H, m-ph), 7.22 (m, 2H, o-ph), 7.19 (m, 1H, p-ph), 7.00 (d, 4 J PH = 3.2 Hz, 1H, m-mes a ), 6.79 (m, 1H, m-mes b ), 6.78 (m, 1H, m -Mes a ), 6.51 (m, 1H, m -Mes b ), 5.88 (br, 1H, 3-CH), 4.14 (br d, J = 10.3 Hz, 1H, 4-CH), 2.62 Mes,b Mes,a Mes,a (s, 3H, o-ch 3 ), 2.45 (s, 3H, o-ch 3 ), 2.34 (m, 1H, 5-CH), 2.26 (s, 3H, p-ch 3 ), 2.15 Mes,b (s, 3H, p-ch 3 ), 2.09 (2H), 1.47 (1H), 1.07 (1H), 1.29 (1H), 0.63 (1H), 1.17 (1H), 0.81 (1H)(each m, CH 2), Mes,b Mes,a 1.96 (s, 3H, o -CH 3 ), 1.83 (s, 3H, o -CH 3 ). 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 213 K): δ (br dm, J = 3.8 Hz, 10-C) t, (br, 2-C) t, (d, 2 J PC = 19.1 Hz, o-mes a ), (i-ph) t, (d, 2 J PC = 6.5 Hz, o-mes b ), (d, 2 J PC = 6.5 Hz, o -Mes a ), (d, 2 J PC = 14.9 Hz, o -Mes b ), (d, 4 J PC = 3.1 Hz, p- Mes a ), (d, 4 J PC = 2.1 Hz, p-mes b ), (d, 3 J PC = 7.2 Hz, m -Mes a ), (d, 3 J PC = 11.2 Hz, m-mes a ), (d, 3 J PC = 7.8 Hz, m-mes b ), (o-ph), (d, 3 J PC = 9.9 Hz, m - Mes b ), (m-ph), (d, 1 J PC = 53.5 Hz, 1-C), (p-ph), (br d, J = 42.7 Hz 3- CH), (d, 1 J PC = 41.9 Hz, i-mes b ), (d, 1 J PC = 25.6 Hz, i-mes a ), 47.9 (d, 3 J PC = 10.9 Hz, S18
19 5-CH), 45.6 (4-CH), 33.5 (dm, J = 6.8 Hz), 27.8, 27.6, 25.8 (CH 2), 25.4 (d, 3 J PC = 10.5 Hz, o- Mes,a CH 3 ), 24.3 (d, 3 Mes,a Mes,b Mes,b J PC = 3.3 Hz, o -CH 3 ), 22.9 (m, o-ch 3 ), 20.7 (m, o -CH 3 ), 20.6 Mes,a Mes,b (d, J = 1.4 Hz, p-ch 3 ), 20.3 (d, J = 1.1 Hz, p-ch 3 ). [C 6F 5 not listed, t tentatively assigned]. 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 213 K): δ 10.4 ( 1/2 ~ 40 Hz) 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 213 K): δ 3.6 (broad). 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 299 K): δ 6.4 ( 1/2 ~ 550 Hz) 19 F NMR (470 MHz, dichloromethane-d 2, 213 K): δ , , , (each br, each 1F, o-c 6F 5), (br t, 3 J FF = 19.7 Hz), (br t, 3 J FF = 20.8 Hz)(each 1F, p-c 6F 5), , (each m, each 2F, m-c 6F 5). Minor component (11 ): 1 H NMR (500 MHz, dichloromethane-d 2, 213 K): δ 7.20 (m, 2H, m-ph), 7.16 (m, 2H, o-ph), 7.14 (m, 1H, p-ph), 7.01 (br, 1H, m-mes a ), 6.94 (br, 1H, m-mes b ), 6.80 (br, 1H, m -Mes a ), 6.47 (br, 1H, m -Mes b ), 5.92 (br, 1H, 3-CH), 3.47 (br m, 1H, 4-CH), 2.78 (m, 1H, 5-CH), 2.76 (s, 3H, Mes,b Mes,a Mes,a Mes,b o-ch 3 ), 2.27 (s, 3H, p-ch 3 ), 2.21 (s, 3H, o-ch 3 ), 2.18 (s, 3H, p-ch 3 ), 2.14 (1H), 1.61 (1H), 1.48 (1H), 1.46 (1H), 1.27 (1H), 1.14 (1H), 1.05 (1H), 0.94 (1H)(each m, CH 2), 1.98 Mes,b Mes,a (s, 3H, o -CH 3 ), 1.76 (s, 3H, o -CH 3 ). 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 213 K): δ (br d, J =.4.2 Hz, 10-C), (d, 2 J PC = 20.0 Hz, o-mes a ), (m, o-mes b ), (i-ph) t, (m, o -Mes b ), (m, p- Mes a ), (d, 2 J PC = 6.5 Hz, o -Mes a ), (m, p-mes b ), (d, 3 J PC = 8.2 Hz, m -Mes a ), (d, 3 J PC = 10.1 Hz, m-mes a ), (d, 3 J PC = 8.2 Hz, m-mes b ), (o-ph), (d, 1 J PC = 53.2 Hz, 1-C), (m, m -Mes b ), (m-ph), (br, 3-CH), (p-ph), (d, 1 J PC = 41.6 Hz, i-mes b ), (d, 1 J PC = 26.6 Hz, i-mes a ), 45.4 (br, 4-CH), 39.8 (d, 3 J PC = 9.6 Hz, 5-CH), 31.7 (d, 3 J PC = 8.2 Hz), 28.5, 25.2, 23.3 (CH 2), 24.2 (d, 3 J PC = 3.3 Hz, o - Mes,a CH 3 ), 24.2 (d, 3 Mes,a Mes,b Mes,b J PC = 9.0 Hz, o-ch 3 ), 21.4 (m, o-ch 3 ), 20.7 (m, o -CH 3 ), 20.6 Mes,a Mes,b (m, p-ch 3 ), 20.4 (p-ch 3 ), n.o. 2-C. [C 6F 5 not listed, t tentatively assigned]. 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 213 K): δ 12.7 (partial relaxed br 1:1:1:1 q, 1 J PB ~ 15 Hz) 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 213 K): δ 3.6 (broad). 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 299 K): δ 6.4 ( 1/2 ~ 550 Hz) 19 F NMR (470 MHz, dichloromethane-d 2, 213 K): δ , , , (each m, each 1F, o-c 6F 5), (br t, 3 J FF = 19.8 Hz), (t, 3 J FF = 20.2 Hz)(each 1F, p-c 6F 5), (2F), (1F), (1F)(each m, m-c 6F 5). S19
20 Figure S19: 1 H NMR (500 MHz, dichloromethane-d2, 213 K) spectrum of compound 11 [admixed with pentane] Figure S20: 13 C{ 1 H} NMR (126 MHz, dichloromethane-d2, 213 K) spectrum of compound 11 [admixed with pentane] S20
21 Figure S21: 19 F NMR (470 MHz, dichloromethane-d2, 213 K) spectrum of compound 11 Figure S22: 31 P{ 1 H} NMR (202 MHz, dichloromethane-d2) spectra of compound 11 at 299 K (1) and 213 K (2). Figure S23: 11 B{ 1 H} NMR (160 MHz, dichloromethane-d2) spectra of compound 11 at 299 K (1) and 213 K (2) S21
22 Figure S24: Dynamic 1 H NMR (500 MHz, dichloromethane-d2) spectra of compound 11 [admixed with pentane] Figure S25: Dynamic 19 F NMR (470 MHz, dichloromethane-d2) spectra of compound 11 S22
23 G [T c, (T)] = RT c( ln(tc/ )) [J/mol] T c= coalescence temperature [K]: 286 K ( 19 F, p-bc 6F 5) = chemical shift difference [Hz]: ( 19 F, p-bc 6F 5, 233 K): 476 Hz R = J/(mol K); 1 J = cal G [286 K, (233 K) = 476 Hz] = J/mol = 12.8 ± 0.3 kcal/mol Crystals suitable for the X-ray crystal structure analysis were obtained by slow diffusion of pentane into a solution of compound 11 in dichloromethane at -35 C: X-ray crystal structure analysis of compound 11: A colorless prism-like specimen of C 46H 38BF 10P C 5H 12, approximate dimensions mm x mm x mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. A total of 346 frames were collected. The total exposure time was 4.33 hours. The frames were integrated with the Bruker SAINT software package using a narrow-frame algorithm. The integration of the data using a monoclinic unit cell yielded a total of reflections to a maximum θ angle of (0.83 Å resolution), of which 7874 were independent (average redundancy 6.145, completeness = 99.9%, R int = 10.95%, R sig = 6.65%) and 5407 (68.67%) were greater than 2σ(F 2 ). The final cell constants of a = (7) Å, b = (9) Å, c = (5) Å, β = (10), volume = (3) Å 3, are based upon the refinement of the XYZ-centroids of 9539 reflections above 20 σ(i) with < 2θ < Data were corrected for absorption effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent transmission was The calculated minimum and maximum transmission coefficients (based on crystal size) are and The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 21/n 1, with Z = 4 for the formula unit, C 46H 38BF 10P C 5H 12. The final anisotropic full-matrix least-squares refinement on F 2 with 620 variables converged at R1 = 5.00%, for the observed data and wr2 = 10.32% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e - /Å 3 and the largest hole was e - /Å 3 with an RMS deviation of e - /Å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 1864 e -. S23
24 Figure S26: X-ray crystal structure of compound 11 (thermal ellipsoids are shown at the 50% probability level) Synthesis of compound 12 Scheme S5 A solution of TEMPO (152.0 mg, mol, 2.0 eq) in benzene (2 ml) was added to a solution of compound 11 (400.0 mg, mol, 1.00 eq) in benzene (3 ml). The reaction mixture was stirred at 60 C for 2 days. Then all volatiles were removed in vacuo and the resulting sticky red residue was dissolved in pentane (3 ml), which was subsequently removed in vacuo. After addition of pentane (3 ml) to the obtained residue the resulting suspension was stored at -35 C for 1 day. Subsequently the off-white solid material was collected and washed with cold pentane (5 x 2 ml) to yield compound 12 as a white fluffy solid (319.2 mg, 0.4 mmol, 80%). S24
25 IR (KBr): ṽ [cm -1 ] = 3688 (m), 3016 (w), 3028 (w), 2935 (m), 2860 (m), 2773 (w), 2739 (w), 2473 (w), 2399 (w), 2348 (w), 2314 (w), 1962 (w), 1886 (w), 1812 (w), 1735 (w), 1642 (s), 1603 (s), 1559 (m), 1515 (s), 1464 (m), 1381 (m), 1324 (w), 1305 (m), 1270 (m), 1260 (m), 1201 (w), 1178 (m), 1160 (m), 1092 (s), 1030 (m), 962 (s), 894 (m), 851 (s), 771 (s), 704 (s), 678 (m), 637 (m), 574 (w), 554 (m), 509 (w), 473 (w), 440 (m), 408 (w). M.p. 136 C. Anal. Calc. for C 46H 36BF 10P: C: 67.33; H: Found: C: 67.65; H: H NMR (500 MHz, dichloromethane-d 2, 299 K): δ 7.42 (3H), 7.34 (3H)(each m, Ph, 3-CH), 6.81 (d, 4 J PH = 3.2 Hz, 4H, m-mes), 2.55 (2H), 2.37 (2H), 1.60 (4H) (each br m, CH 2), 2.25 (s, Mes Mes 6H, p-ch 3 ), 2.09 (s, 12H, o-ch 3 ). 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 299 K): δ (br d, 2 J PC = 30.2 Hz, 2-C), 148.2, (d, J = 2.8 Hz) (d, J = 0.9 Hz), (d, J = 8.5 Hz)(4,5,10-C) t, (dm, 1 J FC~ 240 Hz, C 6F 5), (br d, 2 J PC = 8.9 Hz, o-mes), (d, J = 1.9 Hz, i-ph), (br d, 4 J PC = 2.9 Hz p-mes), (dm, 1 J FC~ 250 Hz, C 6F 5), (dm, 1 J FC~ 250 Hz, C 6F 5), (d, 1 J PC = 53.5 Hz, 1-C) t, (dm, J = 46.2 Hz, 3-CH), (br d, 3 J PC = 8.9 Hz, m-mes), 129.5, 128.4, (p) (Ph), (br, i-c 6F 5), (br dm, 1 J PC = 35.1 Hz, i-mes), 28.7 (d, J = 1.0 Hz), 27.9 (d, J = 4.1 Hz), 23.5, 22.4 (CH 2), 22.8 (br dm, 3 Mes J PC = 5.4 Hz, o-ch 3 ), 20.8 (d, J = 1.4 Hz, Mes p-ch 3 ). [ t tentatively assigned]. 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 299 K): δ 5.8 ( 1/2 ~ 36 Hz). 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 299 K): δ 5.7 ( 1/2 ~ 500 Hz). 19 F NMR (470 MHz, dichloromethane-d 2, 299 K): δ (br, 2F, o-c 6F 5), (t, 1F, 3 J FF = 20.2 Hz, p-c 6F 5), (m, 2F, m-c 6F 5)[ 19 F mp = 6.4]. 1 H NMR (500 MHz, dichloromethane-d 2, 193 K): δ 7.39 (2H), 7.31 (4H)(each m, Ph, 3-CH), 6.94 (d, 4 J PH = 2.3 Hz, 1H, m-mes a ), 6.85 (s, 1H, m -Mes a ), 6.66 (s, 1H, m-mes b ), 6.52 (d, 4 J PH = 2.0 Hz, 1H, m -Mes b ), 2.55 (2H), 2.43 (1H), 1.97 (1H), 1.61 (1H), 1.52 (2H), 1.38 (1H) (each br m, CH 2), Mes,a Mes,b Mes,b 2.25 (s, 3H, p-ch 3 ), 2.09 (s, 3H, p-ch 3 ), 2.06 (s, 3H, o -CH 3 ), Mes,b Mes,a Mes,a 2.03 (s, 3H, o-ch 3 ), 1.96 (s, 3H, o-ch 3 ), 1.83 (s, 3H, o -CH 3 ). 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 193 K): δ (br d, 2 J PC = 30.6 Hz, 2-C), 146.8, 137.7, (d, J = 8.4 Hz)(4,5,10-C) t, (d, 2 J PC = 18.3 Hz, o-mes a ), (o -Mes a ), (m, i-ph), (p-mes a ), (d, 2 J PC = 16.0 Hz, o -Mes b ), (o-mes b ), (m, p-mes b ), (d, 1 J PC = 54.2 Hz, 1-C) t, (br d, 3 J PC = 7.0 Hz, m -Mes a ), (dd, J = 45.0 Hz, J = 12.0 Hz, 3-CH), (br d, 3 J PC = 10.7 Hz, m-mes a ), (d, 3 J PC = 7.4 Hz, m- Mes b ), 128.8, 128.4, 127.8, 127.5, (p) (each br, Ph), (d, 3 J PC = 9.4 Hz, m -Mes b ), (d, 1 J PC = 40.3 Hz, i-mes b ), (d, 1 J PC = 28.5 Hz, i-mes a ), 28.2, 27.2 (d, J = 3.7 Hz), 22.6, 21.5 (CH 2), 24.7 (d, 3 Mes,a J PC = 3.6 Hz, o -CH 3 ), 22.9 (dd, J = 10.1 Hz, J = 4.0 Hz, o- S25
26 Mes,a Mes,b Mes,b Mes,a Mes,b CH 3 ), 21.0 (m, o-ch 3 ), 20.7 (m, o -CH 3 ), 20.5 (p-ch 3 ), 20.0 (p-ch 3 ). [C 6F 5 not listed; t tentatively assigned]. 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 193 K): δ 4.1 ( 1/2 ~ 40 Hz). 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 193 K): δ 2.0 (broad). 19 F NMR (470 MHz, dichloromethane-d 2, 193 K): δ (m, o), (m, o ), (br t, 3 J FF = 21.4 Hz, p), (m, m), (m, m )(each 1F, C 6F 5)[ 19 F mp = 5.6, 5.8], (m, 1F, o), (m, 1F, o ), (br t, 1F, 3 J FF = 21.6 Hz, p), (m, 2F, m,m )(C 6F 5)[ 19 F mp = 7.7]. Figure S27: 1 H NMR (500 MHz, dichloromethane-d2, 193 K) spectrum of compound 12 [admixed with pentane] S26
27 Figure S28: 13 C{ 1 H} NMR (126 MHz, dichloromethane-d2, 193 K) spectrum of compound 12 [admixed with pentane] Figure S29: 19 F NMR (470 MHz, dichloromethane-d2, 193 K) spectrum of compound 12 S27
28 Figure S30: 31 P{ 1 H} NMR (202 MHz, dichloromethane-d2, 193 K) spectrum of compound 12 Figure S31: 11 B{ 1 H} NMR (160 MHz, dichloromethane-d2) spectra of compound 12 at 299 K (1) and 193 K (2) S28
29 Figure S32: Dynamic 1 H NMR (500 MHz, dichloromethane-d2) spectra of compound 12 [admixed with pentane] Figure S33: Dynamic 19 F NMR (470 MHz, dichloromethane-d2) spectra of compound 12 S29
30 G [T c, (T)] = RT c( ln(tc/ )) [J/mol] T c= coalescence temperature [K]: 243 K ( 19 F, p-bc 6F 5) = chemical shift difference [Hz] ( 19 F, p-bc 6F 5, 193 K): 426 Hz R = J/(mol K); 1 J = cal G [243 K, (193 K) = 426 Hz] = J/mol = 10.8 ± 0.3 kcal/mol Crystals suitable for the X-ray crystal structure analysis were obtained by slow diffusion of pentane into a solution of compound 12 in dichloromethane at -35 C: X-ray crystal structure analysis of compound 12: formula C 46H 36BF 10P, M = , colourless crystal, 0.08 x 0.06 x 0.02 mm, a = (3), b = (5), c = (3) Å, β = (1), V = (2) Å 3, ρ calc = gcm -3, μ = mm -1, empirical absorption correction (0.989 T 0.997), Z = 4, monoclinic, space group P2 1/n (No. 14), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), 7819 independent (R int = 0.103) and 5035 observed reflections [I>2σ(I)], 529 refined parameters, R = 0.106, wr 2 = 0.234, max. (min.) residual electron density 0.90 (-0.47) e.å -3, hydrogen atoms were calculated and refined as riding atoms. Figure S34: X-ray crystal structure of compound 12 (thermal ellipsoids are shown at the 30% probability level) S30
31 Synthesis of compound 13 Scheme S6 Phenylacetylene (12.4 mg, 122 µmol, 1.0 eq) was added dropwise to a solution of compound 11 (100 mg, 122 µmol, 1.0 eq) in toluene (4 ml) at ambient temperature and then the reaction mixture was stirred for 16 hours at 80 C. Subsequently all volatiles were removed in vacuo and the resulting yellow oil suspended in pentane (2 ml). Then the reaction suspension was dried in vacuo and the resulting solid was washed with pentane (3 x 2 ml). After drying in vacuo, compound 13 was obtained as a white solid (43.8 mg, 47.4 μmol; 39%). IR (KBr): ṽ [cm -1 ] = 3060 (w), 3027 (w), 2931 (w), 2361 (w) 1945 (w), 1747 (w), 1639 (w), 1603 (w), 1547 (w), 1511 (m), 1452 (s), 1382 (w), 1296 (w), 1269 (m), 1248 (m), 1154 (w), 1083 (s), 1033 (w), 966 (s), 910 (w), 854 (w), 784 (w), 757 (m), 738 (w), 696 (m), 645 (m), 605 (w), 558 (w), 490 (w), 421 (w). M.p. 182 C. Anal. Calc. for C 54H 44BF 10P: C: 70.14; H: Found: C: 68.60; H: H NMR (500 MHz, dichloromethane-d 2, 253 K): δ 9.70 (d, 1 J PH = Hz, PH), 7.31 (m, 2H, o-ph ), 7.30 (m, 2H, m-ph), 7.24 (m, 2H, m-ph ), 7.21 (m, 1H, p-ph ), 7.20 (m, 1H, p-ph), 7.15 (m, 2H, o-ph), 6.91 (br d, 3 J PH = 4.1 Hz, 1H, m-mes a ), 6.84 (br d, 3 J PH = 4.4 Hz, 1H, m- Mes b ), 6.82 (br d, 3 J PH = 3.8 Hz, 1H, m -Mes a ), 6.77 (br d, 3 J PH = 4.6 Hz, 1H, m -Mes b ), 5.90 (br, 1H, 3-CH), 3.82 (dm, 3 Mes,b J HH = 8.8 Hz, 1H, 4-CH), 2.66 (s, 3H, o-ch 3 ), 2.65 (s, 3H, o- Mes,a CH 3 ), 2.52/2.04, 1.72/1.24, 1.63/1.17, 1.47/0.95 (each m, each 1H, CH 2), 2.34 (m, 1H, 5- Mes,b Mes,a Mes,b CH), 2.26 (s, 3H, p-ch 3 ), 2.23 (s, 3H, p-ch 3 ), 1.89 (s, 3H, o -CH 3 ), 1.77 (s, 3H, Mes,a o -CH 3 ). 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 253 K): δ (d, 2 J PC = 7.7 Hz, 10-C) t, (d, 2 J PC = 9.2 Hz, o-mes b ), (d, 4 J PC =2.8 Hz, p-mes a ), (d, 4 J PC = 2.8 Hz, p-mes b ), (d, 2 J PC = 11.0 Hz, o-mes a ), (d, 2 J PC = 9.4 Hz, o -Mes a ), (i-ph), (d, 2 J PC = 10.9 Hz, o -Mes b ), (br dm, J = 14.2 Hz, 3-CH), (d, 3 J PC = 11.3 Hz, m - Mes a ), (d, 3 J PC = 11.5 Hz, m-mes b ), (o-ph ), (d, 3 J PC = 10.8 Hz, m -Mes b ), (d, 3 J PC = 10.7 Hz, m-mes a ), (o-ph), (m-ph), (m-ph ), (i-ph ), (p-ph ), (p-ph), (d, 1 J PC = 77.8 Hz, i-mes a ), (d, 1 J PC = 83.4 Hz, i- S31
32 Mes b ), (d, 1 J PC = 73.1 Hz, 1-C) t, (br 1:1:1:1 q, 1 J CB ~ 80 Hz, BC ), 98.7 (br, PhC ), 51.3 (d, 3 J PC = 12.4 Hz, 5-CH), 43.0 (4-CH), 35.0 (d, 3 J PC = 9.8 Hz), 31.7, 29.2, 26.3 (CH 2), 23.8 (d, 3 Mes,a J PC = 10.7 Hz, o-ch 3 ), 22.3 (d, 3 Mes,a J PC = 5.8 Hz, o -CH 3 ), 21.5 (d, 3 J PC = Mes,b Mes,a Mes,b 4.4 Hz, o-ch 3 ), 21.1 (p-ch 3 ), 20.9 (p-ch 3 ), 20.4 (d, 3 Mes,b J PC = 10.4 Hz, o -CH 3 ), n.o. (2-C). [C 6F 5 not listed; t tentatively assigned]. 31 P NMR (202 MHz, dichloromethane-d 2, 253 K): δ (d, 1 J PH = Hz). 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 253 K): δ ( 1/2 ~ 15 Hz ). 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 253 K): δ 17.7 ( 1/2 ~ 50 Hz) 19 F NMR (470 MHz, dichloromethane-d 2, 253 K): δ (br, 2F, o), (t, 3 J FF = 20.8 Hz, 1F, p), (m, 2F, m)(c 6F 5)[ 19 F mp = 3.2], (m, 2F, o), (t, 3 J FF = 20.7 Hz, 1F, p), (m, 2F, m)(c 6F 5)[ 19 F mp = 4.9]. Figure S35: 1 H NMR (500 MHz, dichloromethane-d2, 253 K) spectrum of compound 13 S32
33 Figure S36: 13 C NMR (126 MHz, dichloromethane-d2, 253 K) spectrum of compound 13 Figure S37: 19 F NMR (470 MHz, dichloromethane-d2, 253 K) spectrum of compound 13 S33
34 Figure S38: 31 P{ 1 H} NMR (1) and 31 P NMR (2) (202 MHz, dichloromethane-d2, 253 K) spectra of compound 13 Figure S39: 11 B{ 1 H} NMR (160 MHz, dichloromethane-d2, 253 K) spectrum of compound 13 Crystals suitable for the X-ray crystal structure analysis were obtained from a dichloromethane solution of compound 13 at -35 C: X-ray crystal structure analysis of compound 13: A colorless prism-like specimen of C 61H 52BF 10P, approximate dimensions mm x mm x mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. A total of 460 frames were collected. The total exposure time was 4.47 hours. The frames were integrated with the Bruker SAINT software package using a narrow-frame algorithm. The integration of the data using a monoclinic unit cell yielded a total of reflections to a maximum θ angle of S34
35 (0.80 Å resolution), of which were independent (average redundancy 3.970, completeness = 99.9%, R int = 5.56%, R sig = 4.69%) and 8954 (87.49%) were greater than 2σ(F 2 ). The final cell constants of a = (7) Å, b = (5) Å, c = (7) Å, β = (2), volume = (2) Å 3, are based upon the refinement of the XYZ-centroids of 9863 reflections above 20 σ(i) with < 2θ < Data were corrected for absorption effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent transmission was The calculated minimum and maximum transmission coefficients (based on crystal size) are and The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 n 1, with Z = 2 for the formula unit, C 61H 52BF 10P. The final anisotropic full-matrix least-squares refinement on F 2 with 669 variables converged at R1 = 3.89%, for the observed data and wr2 = 8.45% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e - /Å 3 and the largest hole was e - /Å 3 with an RMS deviation of e - /Å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 1056 e -. Figure S40: X-ray crystal structure of compound 13 (thermal ellipsoids are shown at the 50% probability level) S35
36 Synthesis of compound 14 Scheme S7 A yellow solution of compound 12 (200.0 mg, mol, 1.0 eq) in CH 2Cl 2 (2 ml) was degassed at -78 C and then exposed to a dihydrogen atmosphere (1.5 bar) at room temperature. The solution was stirred for 24 h at ambient temperature, before all volatiles were removed in vacuo. The obtained off-white residue was washed with pentane (3 x 2 ml) and dried in vacuo to give compound 14 as a white solid (175.7 mg, mol, 88%). IR (KBr): ṽ [cm -1 ] = 3418 (w), 3316 (w), 3055 (w), 3028 (w), 2941 (w), 2854 (w), 2443 (w), 2360 (w), 1939 (w), 1775 (w), 1639 (m), 1604 (m), 1559 (w), 1509 (s), 1461 (s), 1380 (m), 1332 (w), 1293 (w), 1271 (m), 1206 (w), 1176 (w), 1134 (w), 1083 (s), 1030 (m), 967 (s), 905 (m), 857 (m), 768 (m), 741 (w), 698 (m), 678 (w), 647 (m), 617 (w), 575 (w), 555 (m), 512 (w), 488 (w), 429 (m). Decomp. 167 C. Anal. Calc. for C 46H 38BF 10P: C: 67.17; H: Found: C: 67.36; H: H NMR (600 MHz, dichloromethane-d 2, 299 K): δ 9.48 (d, 1 J PH = Hz, 1H, PH), 7.38 (m, 2H, m-ph), 7.31 (m, 1H, p-ph), 7.24 (m, 2H, o-ph), 7.22 (d, 4 J PH = 5.5 Hz, 1H, 3-CH), 7.07 (d, 4 J PH = 4.4 Hz, 1H, m-mes a ), 7.00 (d, 4 J PH = 4.6 Hz, 1H, m-mes b ), 6.96 (d, 1H, 4 J PH = 3.5 Hz, m -Mes a ), 6.81 (d, 4 J PH = 4.4 Hz, 1H, m -Mes b ), 3.90 (partial relaxed 1:1:1:1 q, 1 J BH ~ 85 Hz, 1H, BH), 2.67/ 2.20 (each m, each 1H, 9-CH 2) t, 2.54 (m, 2H, 6-CH 2) t Mes,a, 2.34 (s, 3H, p-ch 3 ), Mes,b Mes,a Mes,b 2.32 (s, 3H, p-ch 3 ), 2.31 (s, 3H, o-ch 3 ), 2.23 (s, 3H, o-ch 3 ), 2.14 (s, 3H, o - Mes,b Mes,a CH 3 ), 1.91 (s, 3H, o -CH 3 ), 1.69 (1H), 1.50 (2H), 1.39 (1H)(each m, 7,8-CH 2) t. [ t tentatively assigned] 13 C{ 1 H} NMR (151 MHz, dichloromethane-d 2, 299 K): δ (d, 4 J PC = 3.9 Hz, 4-C), (d, 4 J PC = 2.8 Hz, p-mes b ), (d, 4 J PC = 3.0 Hz, p-mes a ), (d, 2 J PC = 10.1 Hz, o -Mes b ), (d, 2 J PC = 11.8 Hz, o-mes a ), (d, 2 J PC = 8.4 Hz, o -Mes a ), (d, 2 J PC = 9.9 Hz, o- Mes b ), (d, J = 0.9 Hz, i-ph), (d, 2 J PC = 14.2 Hz, 10-C) t, (br d, 3 J PC = 16.8 Hz, 3-CH), (d, 3 J PC = 12.4 Hz, 5-C) t, (d, 3 J PC = 11.0 Hz, m -Mes a ), (d, 3 J PC = 11.5 Hz, m -Mes b ), (d, 3 J PC = 10.6 Hz, m-mes a ), (d, 3 J PC = 10.5 Hz, m-mes b ), (o-ph), (m-ph), (p-ph), (d, 1 J PC = 83.1 Hz, 1-C), (d, 1 J PC = 76.3 Hz, i- Mes a ), (d, 1 J PC = 80.9 Hz, i-mes b ), 32.1 (d, 3 J PC = 7.7 Hz, 9-CH 2) t, 28.1 (d, 4 J PC = 1.6 Hz, S36
37 6-CH 2) t, 22.5 (7,8-CH 2) t, 22.4 (d, 3 Mes,a Mes,a J PC = 5.2 Hz, o -CH 3 ), 21.4 (d, J = 1.4 Hz, p-ch 3 ), 21.3 (d, 3 Mes,a Mes,b J PC = 11.5 Hz, o-ch 3 ), 21.2 (p-ch 3 ), 21.1 (br d, 3 Mes,b J PC = 6.1 Hz, o -CH 3 ), 21.0 (d, 3 Mes,b J PC = 11.9 Hz, o-ch 3 ), n.o. (2-C).[C 6F 5 not listed; t tentatively assigned] 31 P NMR (243 MHz, dichloromethane-d 2, 299 K): δ (br d, 1 J PH ~ 508 Hz). 31 P{ 1 H} NMR (243 MHz, dichloromethane-d 2, 299 K): δ (m). 11 B NMR (192 MHz, dichloromethane-d 2, 299 K): δ 20.8 (d, 1 J BH ~ 83 Hz) 11 B{ 1 H} NMR (192 MHz, dichloromethane-d 2, 299 K): δ 20.8 ( 1/2 ~ 55 Hz) 19 F NMR (564 MHz, dichloromethane-d 2, 299 K): δ (m, 2F, o), (t, 3 J FF = 20.1 Hz, 1F, p), (m, 2F, m)(c 6F 5)[ 19 F mp = 3.7], (m, 2F, o), (t, 3 J FF = 20.1 Hz, 1F, p), (m, 2F, m)(c 6F 5)[ 19 F mp = 3.6]. Figure S41: 1 H NMR (600 MHz, dichloromethane-d2, 299 K) spectrum of compound 14 S37
38 Figure S42: 13 C{ 1 H} NMR (151 MHz, dichloromethane-d2, 299 K) spectrum of compound 14 Figure S43: 19 F NMR (564 MHz, dichloromethane-d2, 299 K) spectrum of compound 14 Figure S44: 31 P{ 1 H} NMR (1) and 31 P NMR (2) (243 MHz, dichloromethane-d2, 299 K) spectra of compound 14 S38
39 Figure S45: 11 B{ 1 H} NMR (1) and 11 B NMR (2) (192 MHz, dichloromethane-d2, 299 K) spectra of compound 14 Crystals suitable for the X-ray crystal structure analysis were obtained from a solution of compound 14 in dichloromethane at -35 C: X-ray crystal structure analysis of compound 14: formula C 46H 38BF 10P CH 2Cl 2, M = , colourless crystal, 0.07 x 0.06 x 0.04 mm, a = (3), b = (3), c = (5) Å, α = (1), β = (1), γ = (2), V = (1) Å 3, ρ calc = gcm -3, μ = mm -1, empirical absorption correction (0.981 T 0.989), Z = 2, triclinic, space group P1 (No. 2), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), 7274 independent (R int = 0.038) and 4952 observed reflections [I>2σ(I)], 592 refined parameters, R = 0.085, wr 2 = 0.177, max. (min.) residual electron density 0.40 (- 0.29) e.å -3. The hydrogen atoms at P1 and B1 were refined freely; others were calculated and refined as riding atoms. S39
40 Figure S46: X-ray crystal structure of compound 14 (thermal ellipsoids are shown at the 30% probability level) Generation of compound 14-D2 Scheme S8 A yellow solution of compound 12 (20.0 mg, 24.4 mol, 1.0 eq) in CD 2Cl 2 (0.5 ml) was degassed at -78 C using a J-Young NMR tube. Then the solution was exposed to a deuterium gas atmosphere (1.5 bar). After shaking the tube for 16 h at room temperature, the reaction mixture was characterized by NMR experiments. A mixture of compounds 12 and 14-D 2 (12 : 14-D 2 ~ 54 : 46 ( 31 P{ 1 H}) was observed. S40
41 The NMR data of compounds 14-D 2 and 12 are consistent with those listed for isolated compounds 14 and 12 (see above). Compound 14-D 2 2 H NMR (92 MHz, dichloromethane, 299 K): δ 9.46 (d, 1 J PD = 77.1 Hz, 1D, PD), 3.88 (br, 1D, BD). 31 P NMR (243 MHz, dichloromethane-d 2, 299 K): δ (br 1:1:1 t, 1 J PD ~ 79 Hz). 31 P{ 1 H} NMR (243 MHz, dichloromethane-d 2, 299 K): δ (br 1:1:1 t, 1 J PD ~ 79 Hz). 11 B NMR (192 MHz, dichloromethane-d 2, 299 K): δ 21.0 ( 1/2 ~ 70 Hz) 11 B{ 1 H} NMR (192 MHz, dichloromethane-d 2, 299 K): δ 21.0 ( 1/2 ~ 70 Hz) 19 F NMR (564 MHz, dichloromethane-d 2, 299 K): δ , (each m, each 2F, o), , (each t, 3 J FF = 20.1 Hz, each 1F, p), , (each m, each 2F, m)(c 6F 5). Figure S47: 1 H NMR (600 MHz, dichloromethane-d2, 299 K) spectra of (1) the isolated compound 14 and (2) the reaction of compound 12 with D2; (3) 1 H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of the isolated compound 12. S41
42 Figure S48: 19 F NMR (564 MHz, dichloromethane-d2, 299 K) spectra of (1) the isolated compound 14 and (2) the reaction of compound 12 with D2; (3) 19 F NMR (470 MHz, dichloromethane-d2, 299 K) spectrum the isolated compound 12. Figure S49: 2 H NMR (92 MHz, dichloromethane, 299 K) spectrum of the reaction compound 12 with D2 S42
43 Figure S50: (1) 11 B{ 1 H} and (2) 11 B NMR (192 MHz, dichloromethane-d2, 299 K) spectra of the isolated compound 14; (3) 11 B NMR (192 MHz, dichloromethane-d2, 299 K) spectrum of the reaction of compound 12 with D2; (4) 11 B NMR (160 MHz, dichloromethane-d2, 299 K) spectrum of the isolated compound 12 Figure S51: (1) 31 P{ 1 H} and (2) 31 P NMR (243 MHz, dichloromethane-d2, 299 K) spectra of the isolated compound 14; (3) 31 P NMR (243 MHz, dichloromethane-d2, 299 K) spectrum of the reaction of compound 12 with D2; (5) 31 P NMR (202 MHz, dichloromethane-d2, 299 K) spectrum of the isolated compound 12 S43
44 Synthesis of compound 17 Scheme S9 A solution of dimethylacetylenedicarboxylate (17.9 L, 20.7 mg, mol, 1.0 eq) in toluene (1 ml) was added to a solution of compound 11 (120.0 mg, mol, 1.0 eq) in toluene (2 ml). The orange reaction mixture was stirred at 75 C for 6 days. Then all volatiles were removed in vacuo and the resulting sticky residue was dissolved in pentane (5 ml), which was subsequently removed in vacuo. After adding pentane (3 ml) to the obtained sticky solid the resulting suspension was filtered via cannula (Whatman glass fiber filter). The remaining solid was washed with pentane (5 x 3 ml) and dried in vacuo to give compound 17 as a pale yellow solid (70.8 mg, 73.4 mol, 50%). IR (KBr): ṽ [cm -1 ] = 3448 (w), 3193 (w), 3121 (w), 3604 (w), 3029 (m), 2991 (m), 2942 (m), 2862 (m), 2788 (w), 2735 (w), 2688 (w), 2390 (w), 2087 (w), 1946 (w), 1872 (w), 1792 (w), 1736 (s), 1683 (w), 1643 (m), 1605 (m), 1558 (w), 1515 (m),1451 (s), 1041 (w), 1377 (m), 1341 (m), 1276 (m), 1248 (m), 1206 (m), 1180 (w), 1148 (w), 1088 (s), 1030 (m), 972 (s), 926 (w), 859 (m), 801 (w), 783 (m), 741 (m), 691 (s), 658 (m), 642 (s), 616 (w), 654 (m), 525 (w), 460 (w), 435 (w). M.p. 259 C. Anal. Calc. for C 52H 44BF 10O 4P: C: 64.74; H: Found: C: 64.99; H: A solution of the yellow solid in dichloromethane-d 2 showed at 299 K a mixture of two compounds, the major component was assigned as compound 17, the minor one was not identified yet [ratio ca. 64 : 36 ( 31 P)]. [Ar = 4,6-dimethylphenylene] Major component 17: 1 H NMR (600 MHz, dichloromethane-d 2, 299 K): δ 7.23 (m, 2H, m-ph), 7.17 (m, 1H, p-ph), 7.11 (m, 1H, 3-CH Ar ), 7.00 (m, 2H, o-ph), 6.97 (br d, 4 J PH = 5.5 Hz, 1H, 5-CH Ar ), 6.75 (br d, 4 J PH = 2.7 Hz, 1H, m-mes), 6.57 (br d, 4 J PH = 3.9 Hz, 1H, m -Mes), 5.86 (m, 1H, 3-CH), 3.95 (dm, 3 J HH = 10.8 Hz, 1H, 4-CH), 3.68 (s, 3H, OMe C=O ), 3.49 (s, 3H, OMe), 2.72 (s, 3H, o - Mes CH 3 ), 2.55/2.06 (each m, each 1H, 9-CH 2), Ar 2.35 (s, 3H, 4-CH 3 ), 2.35 (m, 1H, 5-CH), 2.25 S44
45 Mes Mes Ar (s, 3H, o-ch 3 ), 2.20 (s, 3H, p-ch 3 ), 2.07 (s, 3H, 6-CH 3 ), 1.91 (s, 3H, CH 3), 1.53, 1.16 (each m, each 1H, 7-CH 2), 1.33/1.02 (each m, each 1H, 6-CH 2), 1.30/0.94 (each m, each 1H, 8-CH 2). 13 C{ 1 H} NMR (151 MHz, dichloromethane-d 2, 299 K): δ (d, 3 J PC = 6.9 Hz, O=C), (d, 2 J PC = 18.3 Hz, O 2C=), (d, 2 J PC = 21.8 Hz, 2-C Ar ), (d, 2 J PC = 6.7 Hz, 10-C), (d, 2 J PC = 10.0 Hz, o-mes), (d, 4 J PC = 2.7 Hz, 4-C Ar ), (d, 2 J PC = 12.7 Hz, o -Mes), (d, 4 J PC = 2.9 Hz, p-mes), (i-ph), (d, 2 J PC = 10.3 Hz, 6-C Ar ), (br, 2-C), (br, 3-CH), (d, 3 J PC = 10.3 Hz, 5-CH Ar ), (d, 3 J PC = 12.3 Hz, m -Mes), (d, 3 J PC = 11.0 Hz, m-mes), (o-ph), (m-ph), (p-ph), (d, 1 J PC = 81.6 Hz, 1-C), (d, 1 J PC = 86.5 Hz, 1-C Ar ), (d, 3 J PC = 10.2 Hz, 3-CH Ar ), (d, 1 J PC = 82.0 Hz, i-mes), 71.8 (d, 1 J PC = Hz, PC=), 56.7 (d, 2 J PC = 15.3 Hz, CMe), 53.7 (OMe), 52.4 (OMe C=O ), 48.4 (d, 3 J PC = 13.0 Hz, 5-CH), 43.8 (d, 4 J PC = 2.1 Hz, 4-CH), 33.5 (d, 3 J PC = 9.4 Hz, 9-CH 2), 29.7 (CH 3), 29.5 (m, 6-CH 2), 28.6 (d, J = 1.5 Hz, 8-CH 2), 26.6 (7-CH 2), 24.9 Mes (m, o -CH 3 ), 23.8 (d, 3 Mes Ar J PC = 6.8 Hz, o-ch 3 ), 21.7 (d, J = 1.3 Hz, 4-CH 3 ), 20.9 (d, 3 J PC = Ar Mes 3.7 Hz, 6-CH 3 ), 20.7 (p-ch 3 ). [C 6F 5 not listed] 31 P{ 1 H} NMR (243 MHz, dichloromethane-d 2, 299 K): δ 15.9 ( 1/2 ~ 4 Hz). 11 B{ 1 H} NMR (192 MHz, dichloromethane-d 2, 299 K): δ 0.8 ( 1/2 ~ 330 Hz). 19 F NMR (564 MHz, dichloromethane-d 2, 299 K): δ (m, o), (m, o ), (t, 3 J FF = 20.2 Hz, p), (m, m ), (m, m)(each 1F, C 6F 5)[ 19 F mp = 4.5, 5.1], (m, o), (m, o ), (t, 3 J FF = 20.4 Hz, p), (m, m ), (m, m)(each 1F, C 6F 5)[ 19 F mp = 3.7, 5.5]. Minor component: 31 P{ 1 H} NMR (243 MHz, dichloromethane-d 2, 299 K): δ 16.5 ( 1/2 ~ 30 Hz). 11 B{ 1 H} NMR (192 MHz, dichloromethane-d 2, 299 K): δ 0.8 ( 1/2 ~ 330 Hz). 19 F NMR (564 MHz, dichloromethane-d 2, 299 K): δ , , , (each br, each 1F, o), , (each br, each 1F, p), not resolved (4F, m)(c 6F 5). S45
46 Figure S52: 1 H NMR (600 MHz, dichloromethane-d2, 299 K) spectrum of compound 17 Figure S53: 13 C{ 1 H} NMR (151 MHz, dichloromethane-d2, 299 K) spectrum of compound 17 S46
47 Figure S54: 19 F NMR (564 MHz, dichloromethane-d2, 299 K) spectrum of compound 17 Figure S55: 31 P{ 1 H} NMR (243 MHz, dichloromethane-d2, 299 K) spectrum of compound 17 Figure S56: 11 B{ 1 H} NMR (192 MHz, dichloromethane-d2, 299 K) spectrum of compound 17 Crystals suitable for the X-ray crystal structure analysis were obtained from a dichloromethane solution of compound 17 at room temperature: X-ray crystal structure analysis of compound 17: A colorless prism-like specimen of C 52H 44BF 10O 4P, approximate dimensions mm x mm x mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. A total of 748 frames S47
48 were collected. The total exposure time was 8.31 hours. The frames were integrated with the Bruker SAINT software package using a narrow-frame algorithm. The integration of the data using a monoclinic unit cell yielded a total of 8271 reflections to a maximum θ angle of (0.84 Å resolution), of which 8271 were independent (average redundancy 1.000, completeness = 99.8%, R int = 8.35%, R sig = 3.22%) and 6534 (79.00%) were greater than 2σ(F 2 ). The final cell constants of a = (7) Å, b = (7) Å, c = (8) Å, β = (10), volume = (4) Å 3, are based upon the refinement of the XYZ-centroids of 9841 reflections above 20 σ(i) with < 2θ < Data were corrected for absorption effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent transmission was The calculated minimum and maximum transmission coefficients (based on crystal size) are and The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 21/n 1, with Z = 4 for the formula unit, C 52H 44BF 10O 4P. The final anisotropic full-matrix least-squares refinement on F 2 with 621 variables converged at R1 = 4.87%, for the observed data and wr2 = 11.16% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e - /Å 3 and the largest hole was e - /Å 3 with an RMS deviation of e - /Å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 1992 e -. Figure S57: X-ray crystal structure of compound 17 (thermal ellipsoids are shown at the 50% probability level) S48
49 Synthesis of compound 18 Scheme S10 A solution of dimethyl acetylenedicarboxylate (18.0 L, 20.8 mg, mol, 1.0 eq) in toluene (1 ml) was added to a solution of compound 12 (120.0 mg, mol, 1.0 eq) in toluene (3 ml) and the reaction mixture was stirred at 100 C for 6 days. Then all volatiles were removed in vacuo and the formed sticky residue was dissolved in pentane (5 ml), which was subsequently removed in vacuo. After adding pentane (3 ml) to the obtained sticky solid the resulting suspension was filtered via cannula (Whatman glass fiber filter). Then the remaining solid was washed with pentane (5 x 3 ml) and dried in vacuo to give compound 18 as a pale orange solid (87.7 mg, 91.1 mol, 62%). IR (KBr): ṽ [cm -1 ] = 3473 (w), 3027 (w), 2938 (m), 2864 (w), 2668 (w), 2540 (w), 2293 (w), 2092 (w), 1744 (s), 1613 (s), 1561 (w), 1515 (s), 1450 (s), 1377 (w), 1338 (m), 1244 (m), 1024 (w), 1150 (w), 1088 (s), 1030 (w), 974 (s), 926 (w), 875 (w), 854 (m), 814 (w), 778 (m), 764 (w), 747 (m), 710 (w), 690 (m), 662 (w), 641 (w), 604 (w), 563 (w), 521 (w), 459 (w), 444 (w), 419 (w). M.p. 268 C. Anal. Calc. for C 52H 42BF 10O 4P: C: 64.88; H: Found: C: 64.91; H: [Ar = 4,6-dimethylphenylene] 1 H NMR (500 MHz, dichloromethane-d 2, 299 K): δ 7.34 (m, 2H, m-ph), 7.27 (m, 1H, p-ph), 7.16 (m, 2H, o-ph), 7.13 (dd, J = 8.1 Hz, J = 5.3 Hz, 1H, 3-CH), 7.04 (m, 1H, 3-CH Ar ), 7.03 (m, 1H, 5-CH Ar ), 6.84 (dm, 4 J PH = 3.6 Hz, 1H, m-mes), 6.42 (dm, 4 J PH = 4.6 Hz, 1H, m -Mes), 3.66 (s, 3H. OMe C=O ), 3.38 (s, 3H, OMe), 2.74/2.28 (each m, each 1H, 9-CH 2) t, 2.55/2.50 (each m, each 1H, 6-CH 2) t Ar Mes, 2.39 (d, J = 0.8 Hz, 3H, 4-CH 3 ), 2.34 (s, 3H, o-ch 3 ) t, 2.20 (s, Mes Ar Mes 3H, p-ch 3 ), 2.09 (s, 3H, 6-CH 3 ), 1.90 (s, 3H, o -CH 3 ) t, 1.59/1.43 (each m, each 1H, 7- CH 2) t, 1.58 (s, 3H, CH 3), 1.51 (m, 2H, 8-CH 2) t. [ t tentatively assigned] 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 299 K): δ (d, 3 J PC = 8.6 Hz, O=C), (d, 2 J PC = 16.3 Hz, O 2C=), (d, 2 J PC = 22.4 Hz, 2-C Ar ), (d, 2 J PC = 9.8 Hz, o-mes) t, (d, 4 J PC = 2.6 Hz, 4-C Ar ), (d, 2 J PC = 12.9 Hz, o -Mes) t, (d, 4 J PC = 3.0 Hz, p- S49
50 Mes), (dd, J = 3.4 Hz, J = 1.1 Hz, 4-C) t, (d, J = 1.2 Hz, i-ph), (d, 2 J PC = 9.9 Hz, 6-C Ar ), (dd, J = 18.5 Hz, J = 9.8 Hz, 3-CH), (d, 1 J PC = 80.8 Hz, 1-C), (d, 2 J PC = 11.3 Hz, 10-C) t, (d, 3 J PC = 11.5 Hz, 5-C) t, (d, 3 J PC = 10.2 Hz, 5- CH Ar ), (d, 3 J PC = 6.2 Hz, m -Mes), (d, 3 J PC = 5.1 Hz, m-mes), (o-ph), (m-ph), (p-ph), (d, 1 J PC = 84.2 Hz, 1-C Ar ), (d, 3 J PC = 10.0 Hz, 3-CH Ar ), (d, 1 J PC = 82.8 Hz, i-mes), 77.8 (d, 1 J PC = Hz, PC=), 55.7 (d, 2 J PC = 15.2 Hz, CMe), 53.7 (d, 4 J PC = 1.2 Hz, OMe), 52.4 (OMe C=O ), 29.4 (d, 3 J PC = 7.1 Hz, 9-CH 2) t, 28.7 (d, 4 J PC = 1.6 Hz, 6-CH 2) t, 28.2 (CH 3), 24.2 (dd, J = 5.8 Hz, J = 3.3 Hz o -Mes) t, 23.9 (dd, J = 7.0 Hz, J = 1.5 Hz, o-mes) t, 23.0 (8-CH 2) t, 22.3 (7-CH 2) t Ar, 21.7 (d, J = 1.3 Hz, 4-CH 3 ), 20.9 (d, 3 Ar J PC = 3.4 Hz, 6-CH 3 ), 20.7 (p-mes), n.o. (2-C). [C 6F 5 not listed; t tentatively assigned] 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 213 K): δ 15.1 ( 1/2 ~ 5 Hz). 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 299 K): δ 1.1 ( 1/2 ~ 350 Hz). 19 F NMR (470 MHz, dichloromethane-d 2, 299 K): δ (m, o), (m, o ), (t, 3 J FF = 20.3 Hz, p), (m, m ), (m, m)(each 1F, C 6F 5)[ 19 F mp = 4.9, 5.5], (m, o), (m, o ), (t, 3 J FF = 20.4 Hz, p), (m, m ), (m, m)(each 1F, C 6F 5)[ 19 F mp = 3.4, 5.8]. Figure S58: 1 H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of compound 18 S50
51 Figure S59: 13 C{ 1 H} NMR (126 MHz, dichloromethane-d2, 299 K) spectrum of compound 18 Figure S60: 19 F NMR (470 MHz, dichloromethane-d2, 299 K) spectrum of compound 18 Figure S61: 31 P{ 1 H} NMR (202 MHz, dichloromethane-d2, 299 K) spectrum of compound 18 S51
52 Figure S62: 11 B{ 1 H} NMR (160 MHz, dichloromethane-d2, 299 K) spectrum of compound 18 Crystals suitable for the X-ray crystal structure analysis were obtained from a dichloromethane solution of compound 18 at -35 C: X-ray crystal structure analysis of compound 18: A colorless plate-like specimen of C 52H 42BF 10O 4P, approximate dimensions mm x mm x mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. A total of 1592 frames were collected. The total exposure time was hours. The frames were integrated with the Bruker SAINT software package using a wide-frame algorithm. The integration of the data using a monoclinic unit cell yielded a total of 8235 reflections to a maximum θ angle of (0.84 Å resolution), of which 8235 were independent (average redundancy 1.000, completeness = 99.8%, R int = 9.30%, R sig = 5.39%) and 6008 (72.96%) were greater than 2σ(F 2 ). The final cell constants of a = (15) Å, b = (17) Å, c = (18) Å, β = (5), volume = (8) Å 3, are based upon the refinement of the XYZ-centroids of 9144 reflections above 20 σ(i) with < 2θ < Data were corrected for absorption effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent transmission was The calculated minimum and maximum transmission coefficients (based on crystal size) are and The final anisotropic full-matrix least-squares refinement on F 2 with 621 variables converged at R1 = 4.81%, for the observed data and wr2 = 12.26% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e - /Å 3 and the largest hole was e - /Å 3 with an RMS deviation of e - /Å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 1984 e -. S52
53 Figure S63: X-ray crystal structure of compound 18 (thermal ellipsoids are shown at the 50% probability level) Synthesis of compound 19 Scheme S11 A solution of compound 11 (200.0 mg, mol, 1.0 eq) in CH 2Cl 2 (1 ml) was degassed at -78 C and exposed to a nitric oxide atmosphere (1.5 bar). The solution turned dark turquoise upon stirring for 15 min. Then all volatiles were removed in vacuo and pentane (3 ml) was added to the obtained residue. The suspension was filtrated via cannula (Whatman glass fiber filter) and the remaining solid was washed with pentane (3 x 2 ml). After drying in vacuo compound 19 was obtained as a pale turquoise solid (166.4 mg, mol, 80%). IR (KBr): ṽ [cm -1 ] = 3515 (w), 3063 (w), 3032 (w), 2937 (m), 2862 (w), 2811 (w), 2349 (w), 2297 (w), 1739 (w), 1644 (s), 1604 (m), 1577 (w), 1553 (w), 1515 (s), 1453 (s), 1382 (m), 1318 (w), S53
54 1280 (m), 1249 (w), 1183 (w), 1149 (w), 1098 (s), 1033 (w), 974 (s), 926 (w), 853 (m), 817 (w), 794 (w), 772 (w), 743 (w), 703 (s), 646 (s), 599 (w), 567 (m), 510 (w), 468 (w). Decomp. 168 C. Anal. Calc. for C 46H 38BF 10PNO: C: 64.80; H: 4.49; N: Found: C: 64.63; H: 4.49; N: Crystals suitable for the X-ray crystal structure analysis were obtained by slow diffusion of pentane into a solution of compound 19 in dichloromethane at -35 C: X-ray crystal structure analysis of compound 19: formula C 46H 38BF 10NOP 2 x CH 2Cl 2, M = , colourless crystal, 0.18 x 0.05 x 0.05 mm, a = (2), b = (2), c = (3) Å, α = (1), β = (1), γ = (2), V = (1) Å 3, ρ calc = gcm -3, μ = mm -1, empirical absorption correction (0.937 T 0.982), Z = 2, triclinic, space group P1 (No. 2), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), 8004 independent (R int = 0.045) and 6444 observed reflections [I>2σ(I)], 657 refined parameters, R = 0.070, wr 2 = 0.161, max. (min.) residual electron density 0.53 (- 0.60) e.å -3, hydrogen atoms were calculated and refined as riding atoms. Figure S64: X-ray crystal structure of compound 19 (thermal ellipsoids are shown at the 30% probability level) S54
55 Synthesis of compound 20 Scheme S12 1,8-Cyclohexadiene (131.6 mg, 1.64 mmol, 10.0 eq) was added to a turquoise solution of compound 19 (140.0 mg, mol, 1.0 eq) in benzene (2 ml) at room temperature. The solution became colorless upon stirring for 1 hour. Then all volatiles were removed in vacuo and the off-white residue crystallized by the layering method with CH 2Cl 2 (1 ml) and pentane (7 ml). The crystalline solid was ground and washed with pentane (3 x 1 ml). After drying in vacuo, compound 20 was obtained as a white solid (88.4 mg, mol, 63%). IR (KBr): ṽ [cm -1 ] = 3515 (m), 3061 (w), 3033 (w), 2936 (m), 2859 (w), 2816 (w), 2733 (w), 2340 (w), 1946 (w), 1640 (m), 1603 (m), 1590 (w), 1554 (w), 1512 (s), 1456 (s), 1406 (w), 1385 (w), 1340 (w), 1276 (m), 1246 (w), 1207 (w), 1162 (w), 1139 (w), 1084 (s), 1040 (m), 967 (s), 927 (w), 892 (w), 852 (m), 803 (w), 779 (w), 754 (w), 741 (w), 703 (m), 689 (m), 645 (s), 599 (w), 572 (m), 510 (w), 473 (w), 452 (w). Decomp. 214 C. Anal. Calc. for C 46H 39BF 10PNO: C: 64.73; H: 4.61; N: Found: C: 64.71; H: 4.50; N: H NMR (500 MHz, dichloromethane-d 2, 299 K): δ 7.33 (m, 2H, m-ph), 7.29 (m, 2H, o-ph), 7.23 (m, 1H, p-ph), 7.00 (d, 4 J PH = 4.3 Hz, 2H, m-mes a ), 6.92 (d, 4 J PH = 4.6 Hz, 2H, m-mes b ), 6.33 (br, 1H, 3-CH), 4.63 (t, J = 9.1 Hz, 1H, OH), 3.89 (br dd, 3 J HH = 9.5 Hz, J = 2.0 Hz, 1H, 4-CH), 2.60/2.13 (each m, each 1H, 9-CH 2), Mes,a Mes,a 2.37 (s, 6H, o-ch 3 ), 2.36 (s, 3H, p-ch 3 ), Mes,b Mes,b 2.33 (m, 1H, 5-CH), 2.29 (s, 3H, p-ch 3 ), 2.20 (s, 6H, o-ch 3 ), 1.56/1.13 (each m, each 1H, 6-CH 2), 1.53/1.14 (each m, each 1H, 7-CH 2), 1.27/0.46 (each m, each 1H, 8-CH 2). 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 299 K): δ (d, 2 J PC = 12.8 Hz, 10-C), (d, 4 J PC = 3.0 Hz, p-mes b ), (d, 2 J PC = 11.4 Hz, o-mes b ), (d, 4 J PC = 2.9 Hz, p-mes a ), (i-ph), (br, 2-C), (d, 2 J PC = 10.4 Hz, o-mes a ), (d, 3 J PC = 11.7 Hz, m- Mes b ), (d, 3 J PC = 11.7 Hz, m-mes a ), (o-ph), (br m, 3-CH), (m-ph), (p-ph), (d, 1 J PC = 86.3 Hz, i-mes a ), (d, 1 J PC = 90.0 Hz, i-mes b ), (d, 1 J PC = 99.3 Hz, 1-C), 50.5 (d, 3 J PC = 13.3 Hz, 5-CH), 44.1 (4-CH), 35.6 (d, 3 J PC = 7.3 Hz, 9-CH 2), 30.2 (br d, 4 J PC = 1.9 Hz, 8-CH 2), 30.0 (br, 6-CH 2), 26.9 (7-CH 2), 24.2 (d, 3 J PC = 4.2 Hz, o- S55
56 Mes,a CH 3 ), 23.8 (d, 3 Mes,b Mes,b J PC = 5.4 Hz, o-ch 3 ), 21.2 (d, J = 1.9 Hz, p-ch 3 ), 21.2 (d, J = 1.3 Hz, Mes,a p-ch 3 ). [C 6F 5 not listed] 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 299 K): δ 28.7 ( 1/2 ~ 25 Hz). 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 299 K): δ 6.6 ( 1/2 ~ 130 Hz) 19 F NMR (470 MHz, dichloromethane-d 2, 299 K): δ (m, 2F, o), (t, 3 J FF = 20.3 Hz, 1F, p), (m, 2F, m)(c 6F 5)[ 19 F mp = 4.4], (m, 2F, o), (t, 3 J FF = 20.3 Hz, 1F, p), (m, 2F, m)(c 6F 5)[ 19 F mp = 2.7]. Figure S65: 1 H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of compound 20 S56
57 Figure S66: 13 C{ 1 H} NMR (126 MHz, dichloromethane-d2, 299 K) spectrum of compound 20 Figure S67: 19 F NMR (470 MHz, dichloromethane-d2, 299 K) spectrum of compound 20 Figure S68 31 P{ 1 H} NMR (202 MHz, dichloromethane-d2, 299 K) spectrum of compound 20 S57
58 Figure S69: 11 B{ 1 H} NMR (160 MHz, dichloromethane-d2, 299 K) spectrum of compound 20 Crystals suitable for the X-ray crystal structure analysis were obtained by slow evaporation from a dichloromethane solution of compound 20: X-ray crystal structure analysis of compound 20: A colorless prism-like specimen of C 46H 39BF 10NOP, approximate dimensions mm x mm x mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. A total of 1605 frames were collected. The total exposure time was hours. The frames were integrated with the Bruker SAINT software package using a wide-frame algorithm. The integration of the data using a monoclinic unit cell yielded a total of reflections to a maximum θ angle of (0.84 Å resolution), of which 7063 were independent (average redundancy 8.098, completeness = 99.2%, R int = 7.46%, R sig = 3.97%) and 5503 (77.91%) were greater than 2σ(F 2 ). The final cell constants of a = (5) Å, b = (6) Å, c = (9) Å, β = (2), volume = (3) Å 3, are based upon the refinement of the XYZ-centroids of 9971 reflections above 20 σ(i) with < 2θ < Data were corrected for absorption effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent transmission was The calculated minimum and maximum transmission coefficients (based on crystal size) are and The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 21/n 1, with Z = 4 for the formula unit, C 46H 39BF 10NOP. The final anisotropic full-matrix least-squares refinement on F 2 with 551 variables converged at R1 = 4.75%, for the observed data and wr2 = 12.71% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e - /Å 3 and the largest hole was e - /Å 3 with an RMS deviation of e - /Å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 1760 e -. S58
59 Figure S70: X-ray crystal structure of compound 20 (thermal ellipsoids are shown at the 50% probability level) Synthesis of compound 21 Scheme S13 A solution of compound 12 (100.0 mg, mol, 1.0 eq) in CH 2Cl 2 (1 ml) was degassed at -78 C and exposed to a nitric oxide atmosphere (1.5 bar). The solution turned dark green upon stirring for 15 min. Then all volatiles were removed in vacuo and pentane (3 ml) was added to the obtained dark green residue. The suspension was filtrated via cannula (Whatman glass fiber filter) and the remaining solid was washed with pentane (3 x 2 ml). After drying in vacuo compound 21 was obtained as a pale green solid (87.4 mg, 91.9 mol, 84%). IR (KBr): ṽ [cm -1 ] = 3518 (w), 3455 (w), 3031 (w), 2940 (m), 2864 (w), 2741 (w), 2624 (w), 2386 (w), 2348 (w), 2302 (w), 1732 (w), 1642 (m), 1604 (m), 1554 (w), 1515 (s), 1459 (s), 1382 (m), 1322 (w), 1283 (m), 1253 (m), 1205 (w), 1178 (w), 1157 (w), 1103 (s), 1029 (w), 974 (s), 926 S59
60 (w), 881 (w), 850 (m), 836 (m), 809 (w), 772 (m), 748 (w), 702 (m), 659 (m), 643 (m), 609 (w), 571 (w), 515 (w), 478 (w), 455 (w), 429 (w). Decomp. 193 C. Anal. Calc. for C 46H 36BF 10PNO: C: 64.96; H: 4.27; N: Found: C: 65.34; H: 4.28; N: Crystals suitable for the X-ray crystal structure analysis were obtained by slow diffusion of pentane into a solution of compound 21 in dichloromethane at -35 C: X-ray crystal structure analysis of compound 21: formula C 46H 36BF 10NOP, M = , pale green crystal, 0.15 x 0.12 x 0.10 mm, a = (3), b = (3), c = (4) Å, β = (1), V = (1) Å 3, ρ calc = gcm -3, μ = mm -1, empirical absorption correction (0.976 T 0.984), Z = 4, monoclinic, space group P2 1/n (No. 14), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), 6794 independent (R int = 0.053) and 5010 observed reflections [I>2σ(I)], 639 refined parameters, R = 0.066, wr 2 = 0.139, max. (min.) residual electron density 0.31 (-0.29) e.å -3, hydrogen atoms were calculated and refined as riding atoms. Figure S71: X-ray crystal structure of compound 21 (thermal ellipsoids are shown at the 30% probability level) S60
61 Synthesis of compound 22 Scheme S14 1,8-Cyclohexadiene (75.4 mg, mol, 10.0 eq) was added to a green solution of compound 21 (80.0 mg, 94.1 mol, 1.0 eq) in benzene (2 ml) at room temperature. The solution became colorless upon stirring for 1 hour. Then all volatiles were removed in vacuo and the remaining off-white residue was washed with pentane (3 x 1 ml). After drying in vacuo, compound 22 was obtained as a white solid (70.8 mg, 83.1 mol, 88%). IR (KBr): ṽ [cm -1 ] = 3494 (w), 2934 (w), 2864 (w), 1642 (m), 1604 (m), 1556 (w), 1515 (s), 1456 (s), 1381 (w), 1342 (w), 1227 (m), 1252 (m), 1212(w), 1159 (w), 1090 (s), 1041 (w), 971 (s), 933 (w), 853 (m), 822 (w), 775 (m), 741 (w), 703 (m), 659 (m), 642 (m), 576 (w), 507 (w), 482 (w), 440 (w). Decomp. 220 C. Anal. Calc. for C 46H 37BF 10PNO: C: 64.88; H: 4.38; N: Found: C: 65.00; H: 4.44; N: H NMR (500 MHz, dichloromethane-d 2, 299 K): δ 7.82 (br, 1H, 3-CH), 7.42 (m, 2H, m-ph), 7.35 (m, 1H, p-ph), 7.33 (m, 2H, o-ph), 6.97 (d, 4 J PH = 4.4 Hz, 4H, m-mes), 4.76 (quint, J = 5.0 Hz, 1H, OH), 2.68 (m, 2H, 9-CH 2), 2.56 (m, 2H, 6-CH 2), Mes 2.33 (s, 6H, p-ch 3 ), 2.13 (s, Mes 12H, o-ch 3 ), 1.67 (m, 2H, 8-CH 2), 1.57 (m, 2H, 7-CH 2). 13 C{ 1 H} NMR (126 MHz, dichloromethane-d 2, 299 K): δ (br, 2-C), (dm, 1 J FC~ 240 Hz, C 6F 5), (dm, (d, 4 J PC = 3.1 Hz, 4-CH), (d, 4 J PC = 2.9 Hz, p-mes), (br d, 2 J PC = 10.8 Hz, o-mes), (d, J = 0.9 Hz, i-ph), (d, 2 J PC = 16.6 Hz, 10-C), (dm, 1 J FC~ 240 Hz, C 6F 5), (dm, 1 J FC~ 250 Hz, C 6F 5), (d, 3 J PC = 12.2 Hz, 5-C), (m, 3-CH), (d, 3 J PC = 11.6 Hz, m-mes), (o-ph), (m-ph), (d, 1 J PC = Hz, 1-C), (br, i-c 6F 5), (p-ph), (d, 1 J PC = 87.4 Hz, i-mes), 30.3 (d, 3 J PC = 5.6 Hz, 9-CH 2), 29.0 (d, 4 J PC = 1.8 Hz, 6-CH 2), 23.5 (br d, 3 Mes J PC = 3.6 Hz, o-ch 3 ), 23.0 (8- CH 2), 22.9 (7-CH 2), Mes 21.2 (d, J = 1.5 Hz, p-ch 3 ). 31 P{ 1 H} NMR (202 MHz, dichloromethane-d 2, 299 K): δ 33.7 ( 1/2 ~ 40 Hz). 11 B{ 1 H} NMR (160 MHz, dichloromethane-d 2, 299 K): δ 5.4 ( 1/2 ~ 150 Hz) 19 F NMR (470 MHz, dichloromethane-d 2, 299 K): δ (br, 2F, o-c 6F 5), (t, 3 J FF = 20.3 Hz, 1F, p-c 6F 5), (m, 2F, m-c 6F 5)[ 19 F mp = 4.2]. S61
62 Figure S72: 1 H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of compound 22 Figure S73: 13 C{ 1 H} NMR (126 MHz, dichloromethane-d2, 299 K) spectrum of compound 22 S62
Reactions of dimethylzirconocene complexes. with a vicinal frustrated P/B Lewis pair
Reactions of dimethylzirconocene complexes with a vicinal frustrated P/B Lewis pair Silke Frömel, Gerald Kehr, Roland Fröhlich, Constantin G. Daniliuc, Gerhard Erker* Organisch-Chemisches Institut der
More informationPhosphirenium-Borate Zwitterion: Formation in the 1,1-Carboboration Reaction of Phosphinylalkynes. Supporting Information
Phosphirenium-Borate Zwitterion: Formation in the 1,1-Carboboration Reaction of Phosphinylalkynes Olga Ekkert, Gerald Kehr, Roland Fröhlich and Gerhard Erker Supporting Information Experimental Section
More informationSupporting Information Borata-alkene Derivatives Conveniently Made by Frustrated Lewis Pair Chemistry
Supporting Information Borata-alkene Derivatives Conveniently Made by Frustrated Lewis Pair Chemistry Juri Möbus 1, Gerald Kehr, Constantin G. Daniliuc $, Roland Fröhlich $, Gerhard Erker* General Procedures.
More informationSupporting Information
Remarkably Variable Reaction Modes of Frustrated Lewis Pairs with Non-Conjugated Terminal Diacetylenes Chao Chen, Roland Fröhlich, Gerald Kehr, Gerhard Erker Organisch-Chemisches Institut, Westfälische
More informationPhospha-Claisen Type Reactions at Frustrated Lewis Pair. Supporting Information
Phospha-Claisen Type Reactions at Frustrated Lewis Pair Frameworks Guo-Qiang Chen, Gerald Kehr, Christian Mück-Lichtenfeld, Constantin G. Daniliuc, Gerhard Erker* Organisch-Chemisches Institut, Universität
More informationSupporting Information
-S1- of 47 Frustrated Lewis Pair Addition to Conjugated Diynes: Formation of Zwitterionic 1,2,3-Butatriene Derivatives Philipp Feldhaus, Birgitta Schirmer, Birgit Wibbeling, Constantin G. Daniliuc, Roland
More informationSupporting Information
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2017 Supporting Information Hydroboration route to geminal P/B frustrated Lewis pairs with
More informationSupporting Information
Anomalous Staudinger reaction at intramolecular frustrated P-B Lewis pair frameworks Annika Stute, Lukas Heletta, Roland Fröhlich, Constantin G. Daniliuc, Gerald Kehr, Gerhard Erker* Organisch-Chemisches
More informationSupporting Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 205 Supporting Information Synthesis and Structures of N-Arylcyano-β-diketiminate Zinc Complexes
More informationSupporting Information
Carbon-Carbon Bond Activation by 1,1-Carboboration of Internal Alkynes Chao Chen, Roland Fröhlich, Gerald Kehr, and Gerhard Erker Organisch-Chemisches Institut, Westfälische Wilehlms-Universität, Corrensstrasse
More informationSupporting Information
1 Supporting Information Reversible Heterolytic Si H Bond Activation by an Intramolecular Frustrated Lewis Pair Wanli Nie a,b, Hendrik F. T. Klare a, Martin Oestreich c, Roland Fröhlich a, Gerald Kehr
More informationSupporting Information
-S1- of 18 Functional Group Chemistry at the Group 4 Bent Metallocene Frameworks: Formation and Metal-free Catalytic Hydrogenation of Bis(imino-Cp)zirconium Complexes Kirill V. Axenov, Gerald Kehr, Roland
More informationWhite Phosphorus is Air-Stable Within a Self-Assembled Tetrahedral Capsule
www.sciencemag.org/cgi/content/full/324/5935/1697/dc1 Supporting Online Material for White Phosphorus is Air-Stable Within a Self-Assembled Tetrahedral Capsule Prasenjit Mal, Boris Breiner, Kari Rissanen,
More informationSupporting Information for the Article Entitled
Supporting Information for the Article Entitled Catalytic Production of Isothiocyanates via a Mo(II) / Mo(IV) Cycle for the Soft Sulfur Oxidation of Isonitriles authored by Wesley S. Farrell, Peter Y.
More informationCoordination Behaviour of Calcocene and its Use as a Synthon for Heteroleptic Organocalcium Compounds
Supporting Information Coordination Behaviour of Calcocene and its Use as a Synthon for Heteroleptic Organocalcium Compounds Reinald Fischer, Jens Langer, Sven Krieck, Helmar Görls, Matthias Westerhausen*
More informationSupporting Information
Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany Carbene Activation of P 4 and Subsequent Derivatization Jason D. Masuda, Wolfgang W. Schoeller, Bruno Donnadieu, and Guy Bertrand * [*] Dr.
More informationSynthesis of Vinyl Germylenes
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supporting Material for Synthesis of Vinyl Germylenes Małgorzata Walewska, Judith Baumgartner,*
More informationSimple Solution-Phase Syntheses of Tetrahalodiboranes(4) and their Labile Dimethylsulfide Adducts
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2017 Supporting Information for: Simple Solution-Phase Syntheses of Tetrahalodiboranes(4) and their
More informationElectronic Supplementary Information (ESI)
Electronic Supplementary Information (ESI) S1 Experimental Section: Materials and methods: All commercially available chemicals were used as supplied without further purification. The Q[5] was synthesized
More informationReversible 1,2-Alkyl Migration to Carbene and Ammonia Activation in an NHC-Zirconium Complex.
Reversible 1,2-Alkyl Migration to Carbene and Ammonia Activation in an NHC-Zirconium Complex. Emmanuelle Despagnet-Ayoub, Michael K. Takase, Jay A. Labinger and John E. Bercaw Contents 1. Experimental
More informationSupporting Information Strong Luminescent Copper(I)-halide Coordination Polymers and Dinuclear Complexes with Thioacetamide and N,N-donor ligands
Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2016 Supporting Information Strong Luminescent Copper(I)-halide Coordination Polymers and Dinuclear
More informationElectronic Supplementary Information
Electronic Supplementary Information Early-Late Heterobimetallic Rh-Ti and Rh-Zr Complexes via Addition of Early Metal Chlorides to Mono- and Divalent Rhodium Dan A. Smith and Oleg V. Ozerov* Department
More informationSupporting Information. Justin M. Salvant, Anne V. Edwards, Daniel Z. Kurek and Ryan E. Looper*
Supporting Information Regioselective base-mediated cyclizations of mono-n-acylpropargylguanadines. Justin M. Salvant, Anne V. Edwards, Daniel Z. Kurek and Ryan E. Looper* * Department of Chemistry, University
More informationSupporting Information
Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Supporting Information Unmasking Representative Structures of TMP-Active Hauser and Turbo Hauser Bases Pablo García-Álvarez, David V. Graham,
More informationSupporting Information
Supporting Information Tris(allyl)indium Compounds: Synthesis and Structural Characterization Ilja Peckermann, Gerhard Raabe, Thomas P. Spaniol and Jun Okuda* Synthesis and characterization Figure S1:
More informationElectronic Supplementary Information. Pd(diimine)Cl 2 Embedded Heterometallic Compounds with Porous Structures as Efficient Heterogeneous Catalysts
Electronic Supplementary Information Pd(diimine)Cl 2 Embedded Heterometallic Compounds with Porous Structures as Efficient Heterogeneous Catalysts Sheng-Li Huang, Ai-Quan Jia and Guo-Xin Jin* Experimental
More informationSupporting Information
Supporting Information Wiley-VCH 2006 69451 Weinheim, Germany A New Melt Approach to the Synthesis of catena- Phosphorus Dications to Access the First Derivatives of 2+ ** [P 6 Ph 4 R 4 ] Jan J. Weigand*,
More informationA Facile and General Approach to 3-((Trifluoromethyl)thio)- 4H-chromen-4-one
A Facile and General Approach to 3-((Trifluoromethyl)thio)- 4H-chromen-4-one Haoyue Xiang and Chunhao Yang* State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy
More informationSupporting Information
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2017 Supporting Information Sulfonato-imino copper(ii) complexes : fast and general Chan-
More informationDavid L. Davies,*, 1 Charles E. Ellul, 1 Stuart A. Macgregor,*, 2 Claire L. McMullin 2 and Kuldip Singh. 1. Table of contents. General information
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
More informationSupporting Information
Supporting Information New Hexaphosphane Ligands 1,3,5-C 6 H 3 {p-c 6 H 4 N(PX 2 ) 2 } 3 [X = Cl, F, C 6 H 3 OMe(C 3 H 5 )]: Synthesis, Derivatization and, Palladium(II) and Platinum(II) Complexes Sowmya
More informationSupporting Information for A Janus-type Bis(maloNHC) and its Zwitterionic Gold and Silver Metal Complexes
Supporting Information for A Janus-type Bis(maloNHC) and its Zwitterionic Gold and Silver Metal Complexes Ashley Carter, Alexander Mason, Michael A. Baker, Donald G. Bettler, Angelo Changas, Colin D. McMillen,
More informationReversible dioxygen binding on asymmetric dinuclear rhodium centres
Electronic Supporting Information for Reversible dioxygen binding on asymmetric dinuclear rhodium centres Takayuki Nakajima,* Miyuki Sakamoto, Sachi Kurai, Bunsho Kure, Tomoaki Tanase* Department of Chemistry,
More informationCatalytic hydrogenation of liquid alkenes with a silica grafted hydride. pincer iridium(iii) complex: Support for a heterogeneous mechanism
Electronic Supplementary Material (ESI) for Catalysis Science & Technology. This journal is The Royal Society of Chemistry 215 Electronic Supplementary Information for Catalysis Science & Technology Catalytic
More informationSupporting Information
Supporting Information Dative Boron-Nitrogen Bonds in Structural Supramolecular Chemistry: Multicomponent Assembly of Prismatic Organic Cages Burcak Icli, Erin Sheepwash, Thomas Riis-Johannessen, Kurt
More informationSupporting Information
Supporting Information The Heptacyanotungstate(IV) Anion: A New 5 d Transition-Metal Member of the Rare Heptacyanometallate Family of Anions Francisco J. Birk, Dawid Pinkowicz, and Kim R. Dunbar* anie_201602949_sm_miscellaneous_information.pdf
More informationA Clipped [3]Rotaxane Derived From Bis-nor-seco-Cucurbit[10]uril
A Clipped [3]Rotaxane Derived From Bis-nor-seco-Cucurbit[10]uril Supplementary Information by James B. Wittenberg, Matthew G. Costales, Peter Y. Zavalij, and Lyle Isaacs* Department of Chemistry and Biochemistry,
More informationBinuclear Rare-Earth Polyhydride Complexes Bearing both
Supporting Information Binuclear Rare-Earth Polyhydride Complexes Bearing both Terminal and Bridging Hydride Ligands Jianhua Cheng, Haiyu Wang, Masayoshi Nishiura and Zhaomin Hou* S1 Contents Experimental
More informationThe oxide-route for the preparation of
Supporting Information for: The oxide-route for the preparation of mercury(ii) N-heterocyclic carbene complexes. Simon Pelz and Fabian Mohr* Fachbereich C-Anorganische Chemie, Bergische Universität Wuppertal,
More informationSupporting Information
Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2015 Supporting Information Single-Crystal-to-Single-Crystal Transformation of an Anion Exchangeable
More informationSupporting Information
Supporting Information Wiley-VCH 2006 69451 Weinheim, Germany Sandwich Complexes Containing Bent Palladium ains Yasuki Tatsumi, Katsunori Shirato, Tetsuro Murahashi,* Sensuke Ogoshi and Hideo Kurosawa*
More informationElectronic Supplementary Information
Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information Synthesis of New Copper(I) Based linear 1-D-Coordination
More informationStoichiometric Reductions of Alkyl-Substituted Ketones and Aldehydes to Borinic Esters Lauren E. Longobardi, Connie Tang, and Douglas W.
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2014 Supplementary Data for: Stoichiometric Reductions of Alkyl-Substituted Ketones and Aldehydes
More informationManganese-Calcium Clusters Supported by Calixarenes
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2014 Manganese-Calcium Clusters Supported by Calixarenes Rebecca O. Fuller, George A. Koutsantonis*,
More informationPrabhat Gautam, Bhausaheb Dhokale, Shaikh M. Mobin and Rajneesh Misra*
Supporting Information Ferrocenyl BODIPYs: Synthesis, Structure and Properties Prabhat Gautam, Bhausaheb Dhokale, Shaikh M. Mobin and Rajneesh Misra* Department of Chemistry, Indian Institute of Technology
More informationThe CB[n] Family: Prime Components for Self-Sorting Systems Supporting Information
The CB[n] Family: Prime Components for Self-Sorting Systems Supporting Information by Simin Liu, Christian Ruspic, Pritam Mukhopadhyay,Sriparna Chakrabarti, Peter Y. Zavalij, and Lyle Isaacs* Department
More informationSupporting Information
Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Facile Heterolytic H 2 Activation by Amines and B(C 6 F 5 ) 3 Victor Sumerin, Felix Schulz, Martin Nieger, Markku Leskelä, Timo Repo,* and
More informationElectronic Supplementary Information for: Gram-scale Synthesis of a Bench-Stable 5,5 -Unsubstituted Terpyrrole
Electronic Supplementary Information for: Gram-scale Synthesis of a Bench-Stable 5,5 -Unsubstituted Terpyrrole James T. Brewster II, a Hadiqa Zafar, a Matthew McVeigh, a Christopher D. Wight, a Gonzalo
More informationSupporting Information
Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013 Tuning the Lewis Acidity of Boranes in rustrated Lewis Pair Chemistry: Implications for the Hydrogenation of Electron-Poor
More informationSupporting Information for
Supporting Information for Tris(carbene)borate ligands featuring imidazole-2-ylidene, benzimidazol-2-ylidene and 1,3,4-triazol-2-ylidene donors. Evaluation of donor properties in four-coordinate {NiNO}
More informationHydrophobic Ionic Liquids with Strongly Coordinating Anions
Supporting material Hydrophobic Ionic Liquids with Strongly Coordinating Anions Hasan Mehdi, Koen Binnemans*, Kristof Van Hecke, Luc Van Meervelt, Peter Nockemann* Experimental details: General techniques.
More informationAnion binding vs deprotonation in colorimetric pyrrolylamido(thio)urea based anion sensors
Anion binding vs deprotonation in colorimetric pyrrolylamido(thio)urea based anion sensors Louise S. Evans, ilip A. Gale *, Mark E. Light and Roberto Quesada * School of Chemistry, University of Southampton,
More informationSupplementary Materials for
www.advances.sciencemag.org/cgi/content/full/1/5/e1500304/dc1 Supplementary Materials for Isolation of bis(copper) key intermediates in Cu-catalyzed azide-alkyne click reaction This PDF file includes:
More informationorganic papers 2-[(Dimethylamino)(phenyl)methyl]benzoic acid
organic papers Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 2-[(Dimethylamino)(phenyl)methyl]benzoic acid Yvette L. Dann, Andrew R. Cowley and Harry L. Anderson* University
More informationEfficient, scalable and solvent-free mechanochemical synthesis of the OLED material Alq 3 (q = 8-hydroxyquinolinate) Supporting Information
Efficient, scalable and solvent-free mechanochemical synthesis of the OLED material Alq 3 (q = 8-hydroxyquinolinate) Xiaohe Ma, Gin Keat Lim, Kenneth D.M. Harris, David C. Apperley, Peter N. Horton, Michael
More informationScandium and Yttrium Metallocene Borohydride Complexes: Comparisons of (BH 4 ) 1 vs (BPh 4 ) 1 Coordination and Reactivity
Scandium and Yttrium Metallocene Borohydride Complexes: Comparisons of (BH 4 ) 1 vs (BPh 4 ) 1 Coordination and Reactivity Selvan Demir, Nathan A. Siladke, Joseph W. Ziller, and William J. Evans * Department
More informationSupporting Information. for
Supporting Information for "Inverse-Electron-Demand" Ligand Substitution in Palladium(0) Olefin Complexes Shannon S. Stahl,* Joseph L. Thorman, Namal de Silva, Ilia A. Guzei, and Robert W. Clark Department
More informationSupplementary Information: Selective Catalytic Oxidation of Sugar Alcohols to Lactic acid
Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 2014 Supplementary Information: Selective Catalytic Oxidation of Sugar Alcohols to Lactic acid
More informationA Facile Route to Rare Heterobimetallic Aluminum-Copper. and Aluminum-Zinc Selenide Clusters
Supporting Information For A Facile Route to Rare Heterobimetallic Aluminum-Copper and Aluminum-Zinc Selenide Clusters Bin Li, Jiancheng Li, Rui Liu, Hongping Zhu*, and Herbert W. Roesky*, State Key Laboratory
More informationTotal Synthesis of Gonytolides C and G, Lachnone C, and. Formal Synthesis of Blennolide C and Diversonol
. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry Total Synthesis of Gonytolides C and G, Lachnone C, and Formal Synthesis
More informationZiessel a* Supporting Information (75 pages) Table of Contents. 1) General Methods S2
S1 Chemistry at Boron: Synthesis and Properties of Red to Near-IR Fluorescent Dyes based on Boron Substituted Diisoindolomethene Frameworks Gilles Ulrich, a, * Sebastien Goeb a, Antoinette De Nicola a,
More informationSupporting Information
Submitted to Cryst. Growth Des. Version 1 of August 22, 2007 Supporting Information Engineering Hydrogen-Bonded Molecular Crystals Built from 1,3,5-Substituted Derivatives of Benzene: 6,6',6''-(1,3,5-Phenylene)tris-1,3,5-triazine-2,4-diamines
More informationSupporting Information
Supporting Information Calix[4, 5]tetrolarenes: A New Family of Macrocycles Yossi Zafrani* and Yoram Cohen* School of Chemistry, The Sackler Faculty of Exact Sciences, Tel Aviv University, Ramat Aviv 69978,
More informationIron Complexes of a Bidentate Picolyl NHC Ligand: Synthesis, Structure and Reactivity
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2016 Supplementary Information for Iron Complexes of a Bidentate Picolyl HC Ligand: Synthesis,
More informationSupporting Information. Chiral phosphonite, phosphite and phosphoramidite η 6 -areneruthenium(ii)
Supporting Information Chiral phosphonite, phosphite and phosphoramidite η 6 -areneruthenium(ii) complexes: application to the kinetic resolution of allylic alcohols. Mariano A. Fernández-Zúmel, Beatriz
More informationSynthetic, Structural, and Mechanistic Aspects of an Amine Activation Process Mediated at a Zwitterionic Pd(II) Center
Synthetic, Structural, and Mechanistic Aspects of an Amine Activation Process Mediated at a Zwitterionic Pd(II) Center Supporting Information Connie C. Lu and Jonas C. Peters* Division of Chemistry and
More informationSupplemental Information
Supplemental Information Template-controlled Face-to-Face Stacking of Olefinic and Aromatic Carboxylic Acids in the Solid State Xuefeng Mei, Shuanglong Liu and Christian Wolf* Department of Chemistry,
More informationSpain c Departament de Química Orgànica, Universitat de Barcelona, c/ Martí I Franqués 1-11, 08080, Barcelona, Spain.
a Institute of Chemical Research of Catalonia, Av. Països Catalans, 16, 43007 Tarragona, Spain. b Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, E-08193 Barcelona, Spain
More informationTransformations: New Approach to Sampagine derivatives. and Polycyclic Aromatic Amides
-1- An Unexpected Rearrangement which Disassembles Alkyne Moiety Through Formal Nitrogen Atom Insertion between Two Acetylenic Carbons and Related Cascade Transformations: New Approach to Sampagine derivatives
More informationReactivity of (Pyridine-Diimine)Fe Alkyl Complexes with Carbon Dioxide. Ka-Cheong Lau, Richard F. Jordan*
Supporting Information for: Reactivity of (Pyridine-Diimine)Fe Alkyl Complexes with Carbon Dioxide Ka-Cheong Lau, Richard F. Jordan* Department of Chemistry, The University of Chicago, 5735 South Ellis
More informationSelective total encapsulation of the sulfate anion by neutral nano-jars
Supporting Information for Selective total encapsulation of the sulfate anion by neutral nano-jars Isurika R. Fernando, Stuart A. Surmann, Alexander A. Urech, Alexander M. Poulsen and Gellert Mezei* Department
More informationoligomerization to polymerization of 1-hexene catalyzed by an NHC-zirconium complex
Mechanistic insights on the controlled switch from oligomerization to polymerization of 1-hexene catalyzed by an NHC-zirconium complex Emmanuelle Despagnet-Ayoub, *,a,b Michael K. Takase, c Lawrence M.
More informationSupplementary Figure S1 a, wireframe view of the crystal structure of compound 11. b, view of the pyridinium sites. c, crystal packing of compound
a b c Supplementary Figure S1 a, wireframe view of the crystal structure of compound 11. b, view of the pyridinium sites. c, crystal packing of compound 11. 1 a b c Supplementary Figure S2 a, wireframe
More informationSupporting Information. Ze-Min Zhang, Lu-Yi Pan, Wei-Quan Lin, Ji-Dong Leng, Fu-Sheng Guo, Yan-Cong Chen, Jun-Liang Liu, and Ming-Liang Tong*
Supporting Information Wheel-shaped nanoscale 3d-4f {Co II 16Ln III 24} clusters (Ln = Dy and Gd) Ze-Min Zhang, Lu-Yi Pan, Wei-Quan Lin, Ji-Dong Leng, Fu-Sheng Guo, Yan-Cong Chen, Jun-Liang Liu, and Ming-Liang
More informationb = (9) Å c = (7) Å = (1) V = (16) Å 3 Z =4 Data collection Refinement
organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 8-Iodoquinolinium triiodide tetrahydrofuran solvate Jung-Ho Son and James D. Hoefelmeyer* Department of Chemistry,
More informationmetal-organic compounds
metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 Poly[tetra-l-cyanido-dipyridinecadmium(II)zinc(II)] Sheng Li,* Kun Tang and Fu-Li Zhang College of Medicine,
More information1,4-Dihydropyridyl Complexes of Magnesium: Synthesis by Pyridine. Insertion into the Magnesium-Silicon Bond of Triphenylsilyls and
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2018 Electronic Supporting Information 1,4-Dihydropyridyl Complexes of Magnesium: Synthesis
More informationStereoselective Synthesis of (-) Acanthoic Acid
1 Stereoselective Synthesis of (-) Acanthoic Acid Taotao Ling, Bryan A. Kramer, Michael A. Palladino, and Emmanuel A. Theodorakis* Department of Chemistry and Biochemistry, University of California, San
More informationCarbon monoxide and carbon dioxide insertion chemistry of f-block N-heterocyclic carbene complexes. Experimental details and characterising data
Carbon monoxide and carbon dioxide insertion chemistry of f-block N-heterocyclic carbene complexes Polly L. Arnold,* a Zoe R. Turner, a,b Ian J. Casely, a,c Ronan Bellabarba, c and Robert P. Tooze c Experimental
More informationSupporting Text Synthesis of (2 S ,3 S )-2,3-bis(3-bromophenoxy)butane (3). Synthesis of (2 S ,3 S
Supporting Text Synthesis of (2S,3S)-2,3-bis(3-bromophenoxy)butane (3). Under N 2 atmosphere and at room temperature, a mixture of 3-bromophenol (0.746 g, 4.3 mmol) and Cs 2 C 3 (2.81 g, 8.6 mmol) in DMS
More informationSupporting Information
Supporting Information Heteroligand o-semiquinonato-formazanato cobalt complexes Natalia A. Protasenko, Andrey I. Poddel sky,*, Artem S. Bogomyakov, Georgy K. Fukin, Vladimir K. Cherkasov G.A. Razuvaev
More informationSupporting Information for
Supporting Information for Nickel(I)-mediated transformations of carbon dioxide in closed synthetic cycles: reductive cleavage and coupling of CO 2 generating Ni I CO, Ni II CO 3 and Ni II C 2 O 4 Ni II
More informationElectronic Supporting Information
Electronic Supporting Information Solid-State Coexistence of {Zr 12 } and {Zr 6 } Zirconium Oxocarboxylate Clusters Iurie L. Malaestean, Meliha Kutluca Alıcı, Claire Besson, Arkady Ellern and Paul Kögerler*
More information2-(2 -pyridyl)-4,6-diphenylphosphinine versus 2-(2 -pyridyl)-4,6- diphenylpyridine: An evaluation of their coordination chemistry towards Rh(I)
Supplementary Material (ESI) for New Journal of Chemistry This journal is (c) The Royal Society of Chemistry and The Centre National de la Recherche Scientifique, 2010 2-(2 -pyridyl)-4,6-diphenylphosphinine
More informationSupporting Information. Molecular Iodine-Catalyzed Aerobic α,β-diamination of Cyclohexanones with 2- Aminopyrimidine and 2-Aminopyridines
Supporting Information Molecular Iodine-Catalyzed Aerobic α,β-diamination of Cyclohexanones with 2- Aminopyrimidine and 2-Aminopyridines Thanh Binh guyen,* Ludmila Ermolenko, Pascal Retailleau, and Ali
More informationSupporting Information
Supporting Information α-dicationic Chelating Phosphines: Synthesis and Application to the Hydroarylation of Dienes Lianghu Gu, Lawrence M. Wolf, Adam Zieliński, Walter Thiel and Manuel Alcarazo e-mail:
More informationElectronic Supplementary Information
Electronic Supplementary Information Synthesis of borasiloxane-based macrocycles by multicomponent condensation reactions in solution or in a ball mill Mirela Pascu, Albert Ruggi, Rosario Scopelliti, and
More informationSupporting Information
Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2015 A rare case of a dye co-crystal showing better dyeing performance Hui-Fen Qian, Yin-Ge Wang,
More information,
2013. 54, 6. 1115 1120 UDC 548.737:547.12 CHARACTERIZATION AND CRYSTAL STRUCTURES OF SOLVATED N -(4-HYDROXY-3-NITROBENZYLIDENE)-3-METHYLBENZOHYDRAZIDE AND N -(4-DIMETHYLAMINOBENZYLIDENE)-3-METHYLBENZOHYDRAZIDE
More informationElectronic Supplementary Information
Electronic Supplementary Information Thermally Reversible Single-Crystal to Single-Crystal Transformation of Mononuclear to Dinuclear Zn(II) Complexes By[2+2] Cycloaddition Reaction Raghavender Medishetty,
More informationDiastereoselectivity in the Staudinger reaction of. pentafluorosulfanylaldimines and ketimines
Supporting Information for Diastereoselectivity in the Staudinger reaction of pentafluorosulfanylaldimines and ketimines Alexander Penger, Cortney. von ahmann, Alexander S. Filatov and John T. Welch* Address:
More informationEur. J. Inorg. Chem WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2013 ISSN SUPPORTING INFORMATION
Eur. J. Inorg. Chem. 2013 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013 ISSN 1099 0682 SUPPORTING INFORMATION DOI: 10.1002/ejic.201300309 Title: Hydrogen Evolution Catalyzed by Aluminum-Bridged
More informationHalogen bonded dimers and ribbons from the self-assembly of 3-halobenzophenones Patricia A. A. M. Vaz, João Rocha, Artur M. S. Silva and Samuel Guieu
Electronic Supplementary Material (ES) for CrystEngComm. This journal is The Royal Society of Chemistry 27 Halogen bonded dimers and ribbons from the self-assembly of -halobenzophenones Patricia A. A.
More informationSelective Reduction of a Pd Pincer PCP Complex to Well- Defined Pd(0) Species
1 Selective Reduction of a Pd Pincer PCP Complex to Well- Defined Pd(0) Species Luis M. Martínez-Prieto, a Cristóbal Melero, a Pilar Palma, a Diego del Río, b Eleuterio Álvarez a and Juan Cámpora a, *.
More informationActive Trifluoromethylating Agents from Well-defined Copper(I)-CF 3 Complexes
Supplementary Information Active Trifluoromethylating Agents from Well-defined Copper(I)-CF 3 Complexes Galyna Dubinina, Hideki Furutachi, and David A. Vicic * Department of Chemistry, University of Hawaii,
More informationSupporting Information
Selective Hg 2+ sensing behaviors of rhodamine derivatives with extended conjugation based on two successive ring-opening processes Chunyan Wang a,b and Keith Man-Chung Wong a,b * a Department of Chemistry,
More informationSupporting Information
Supporting Information Manuscript Title: Synthesis of Semibullvalene Derivatives via Co 2 (CO) 8 -Mediated Cyclodimerization of 1,4-Dilithio-1,3-butadienes Corresponding Author: Zhenfeng Xi Affiliations:
More informationData collection. Refinement. R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 92 parameters
organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 1,1 0 -(Butane-1,4-diyl)dipyridinium dibromide dihydrate Ming-Qiang Wu, a Xin Xiao, a Yun-Qian Zhang, a * Sai-Feng
More informationA Highly Reactive Scandium Phosphinoalkylidene Complex: C H and H H Bonds Activation
A Highly Reactive Scandium Phosphinoalkylidene Complex: C H and H H Bonds Activation Weiqing Mao, Li Xiang, Carlos Alvarez Lamsfus, Laurent Maron,*, Xuebing Leng, Yaofeng Chen*, State Key Laboratory of
More informationZ =8 Mo K radiation = 0.35 mm 1. Data collection. Refinement. R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections
organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 4-Amino-3-(4-pyridyl)-1,2,4-triazole- 5(4H)-thione Fang Zou, Wei-Min Xuan, Xue-Ming Fang and Hui Zhang* State
More information