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1 -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 Fröhlich, Stefan Grimme, Gerald Kehr, Gerhard Erker Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, Münster, Germany Supporting Information Table of Contents General Information Materials Experimental Procedures S2 S2 S3

2 -S2- of 47 General Information. All reactions were carried out under argon atmosphere with Schlenk-type glassware. Solvents were dried using a Grubbs-type system [Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, ], which uses activated basic alumina and/or molecular sieves as drying agents in combination with copper metal as oxygen scavenger. Pentane and methylene dichloride, were dried in this manner. The following instruments were used for physical characterization of the compounds. Elemental analyses: Foss-Heraeus CHN-O-Rapid. NMR: Varian Inova 500 ( 1 H, 500 MHz; 13 C, 126 MHz, 31 P, 202 MHz, 11 B, 160 MHz, 19 F, 470 MHz), Varian UnityPlus 600 ( 1 H, 600 MHz; 13 C, 151 MHz, 31 P, 242 MHz, 11 B, 192 MHz, 19 F, 564 MHz), Bruker AV300 ( 1 H, 300 MHz, 13 C, 76 MHz, 31 P, 122 MHz, 11 B, 96 MHz, 19 F, 282 MHz). Assignments of the resonances were supported by 2D experiments. X-Ray diffraction: Data sets were collected with a Nonius KappaCCD diffractometer. Programs used: data collection, COLLECT (Nonius B.V., 1998); 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). Thermals ellipsoids are shown with 50% probability, R- values are given for observed reflections, and wr 2 values are given for all reflections. Exceptions and special features: For the compound trans-6 an unidentified disordered solvent molecule was found in the asymmetrical unit and could not be satisfactorily refined. The program SQUEEZE (A. L. Spek J. Appl. Cryst., 2003, 36, 7-13) was therefore used to remove mathematically the effect of the solvent. One n- Propyl group (C5, C6 and C7 atoms) is disordered over two positions. Several restraints (SADI, SIMU and SAME) were used in order to improve refinement stability. Compound 7 present two tert-butyl groups (C22, C23, C24, C32, C33 and C34 atoms) disordered over two positions. Several restraints (SADI, EADP) were used in order to improve refinement stability. The hydrogen of the P1 atom in compound 9 was refined freely, but with fixed U-value. IR spectra were recorded as KBr-pellets or as pure compounds using an ATR-unit on a Varian 3100 FT-IR (Excalibur Series) spectrometer. For the determination of melting points a DSC Q 20 (TA Instruments) was employed Materials. Tris(pentafluorphenyl)borane was prepared according to literature procedure 1. 1 a) A. G. Massey, A. J. Park, J. Organomet. Chem. 1966, 5, ; b) A. G. Massey, A. J. Park, J. Organomet. Chem. 1964, 2, , c) A. G. Massey, A. J. Park, F. G. A. Stone, Proc. Chem. Soc. 1963, 212.

3 -S3- of 47 Experimental procedures. Compound 5 B(C 6 F 5 ) 3 (256 mg, mmol, 1.00 eq) was dissolved in n-pentane (10 ml). In a small Schlenk tube tri-orthotolylphosphane (152 mg, mmol, 1.00 eq) was dissolved in n-pentane (5 ml) and 4,6-decadiyne (67.1 mg, 81.8 µl, mmol, 1 eq) was added. Afterwards the solution was added to the borane solution via syringe. The yellowish mixture was stirred for four days at room temperature. The product grew in small crystals on the glass bottom. The overlaying solution was decanted, the obtained residue washed with n-pentane (once 6 ml) and dried in vacuo (yield 86.3 mg, 18 %). Crystals suitable for X-ray crystal structure analysis were obtained by diffusion method of a dichloromethane/pentane solution at 40 C. Anal. Calc. for C 49 H 35 BF 15 P: C 61.91, H 3.71; found: C 61.45, H IR (KBr): ~ υ = 4128 (w), 3853 (w), 3801 (w), 3750 (w), 3675 (w), 3648 (w), 3192 (w), 3137 (m), 3065 (s), 3014 (m), 2972 (s), 2947 (m), 2873 (m), 2829 (w), 2729 (w), 2663 (w), 2628 (w), 2590 (w), 2551 (w) 2487 (w), 2357 (m), 2209 (m), 2090 (w), 2040 (m) (w), 1948 (m), 1917 (w), 1863 (w), 1830 (w), 1800 (w), 1772 (w), 1717 (m), 1700 (m), 1645 (s), 1594 (m), 1568 (m), 1525 (w), 1430 (w), 1375 (m), 1337 (w), 1274 (m), 1202 (m), 1170 (m), 1137 (m), 1071 (m), 1030 (m), 964 (m), 913 (m), 876 (m), 832 (w), 807 (s). M. p.: 180 C (DSC) 1 H NMR (500 MHz, [D 2 ]-dichloromethane, 233 K): δ = 8.39 (m, 1H, [B] P (C 6 F 5 ) 3 B o m p 3 o' m' [P] o -Tol a ), 7.69 (m, 1H, p-tol a ), 7.67 (m, 1H, m -Tol a ) 7.64 (m, 1H, p-tol c ), 7.56 (m, 1H, m-tol c ), 7.46 (m, 1H, p-tol b ), 7.45 (m, 1H, o -Tol c ), 7.33 (m, 3H, m-tol a, o -Tol b, m -Tol c ), 7.21 (m, 2H, m-tol b, m -Tol b ), 2.58 (m, 1H, = CH [B] 2 ), 2.30 (m, 1H, = CH 2 [B] ), 2.21 (s, 3H, o-tol CH3c ), 1.87 (s, 3H, o-tol CH3b ), 1.68 (m, 1H, CH [P] 2 ), 1.61 (s, 3H, o-tol CH3a ), 1.54 (m, 1H, CH 2 [P] ), 0.82 (m, 1H, CH [P] 2 ), 0.68 (m, 1H, CH 2 [P] ), 0.46 (m, 1H, CH 2 [B] ), 0.39 (t, 3 J HH = 7.0 Hz, 3H, CH [P] 3 ), 0.04 (t, 3 J HH = 7.0 Hz, 3H, CH [B] 3 ), 0.79 (m, 1H, CH [B] 2 ). 13 C{ 1 H} NMR (126 MHz, [D 2 ]-dichloromethane, 233 K): δ = (m, =C B ), (d, 1 J PC = 9.4 Hz, o-tol c ), (d, 1 J PC = 7.4 Hz, o-tol b ), (d, 1 J PC = 7.5 Hz, o-tol a ), (m, o -Tol a ), (d, 1 J CH = 11.1 Hz, o -Tol b ), (d, 4 J PC = 2.7 Hz, p-tol a ), (d, 1 J CH = 11.7 Hz, o -Tol c ), (d, 4 J PC = 2.7 Hz, p-tol c ), (d, 4 J PC = 2.7 Hz, p-tol b ), (d, 3 J PC 11 Hz, m-tol c ), (d, 3 J PC 11 Hz, m-tol a ), (d, 3 J PC = 10.9 Hz, m-tol b ), (d, 3 J PC = 12.5 Hz, m -Tol c ), (d, 3 J PC = 13.2 Hz, m -Tol a ), (d, 3 J PC = 12.7 Hz, m -Tol b ), (d, 1 J PC 88 Hz, i-tol b ), (d, 1 J PC 80 Hz, i-tol c ), (d, 1 J PC 80 Hz, i-tol a ), (dm, 1 J PC = 77.1 Hz, =C P ), 99.6 (d, J = 10.2 Hz,, C CH2 ), 78.7 (d,

4 -S4- of 47 J = 18.0 Hz,, C), 46.9 (m, = CH [B] 2 ), 23.1 (m, o-tol CH3b ), 22.9 (d, 4 J PC = 3.3 Hz, o-tol CH3a ), 22.8 (d, 4 J PC = 4.0 Hz, o-tol CH3c ), 21.5 (d, J = 17.2 Hz, CH [B] 2 ), 20.9 ( CH [P] 2 ), 20.9 (CH [P] 2 ), 15.1 (d, J = 4.0 Hz, CH [B] 3 ), 12.7 (CH [P] 3 ), [C 6 F 5 not listed]. 31 P NMR (202 MHz, [D 2 ]-dichloromethane, 233 K): δ = 21.2 (br s, ν 1/2 60 Hz). 31 P{ 1 H} NMR (202 MHz, [D 2 ]-dichloromethane, 233 K): δ = 21.2 (m). 11 B{ 1 H} NMR (160 MHz, [D 2 ]-dichloromethane, 233 K): δ = 14.0 (ν 1/2 40 Hz). 19 F NMR (470 MHz, [D 2 ]-dichloromethane, 233 K): δ = (o), (o ), (p), (m), (m ), (each m, each 1F, C 6 F a 5 ), [ δ 19 F m,p = 5.8, 6.2]; (o), (o ), (p), (m ), (m), (each m, each 1F, C 6 F b 5 ), [ δ 19 F m,p = 3.9, 4.6]; (o), (o ), (p), (m ), (m), (each m, each 1F, C 6 F c 5 ), [ δ 19 F m,p = 4.2, 4.3]. 19 F, 19 F GCOSY (470 MHz / 470 MHz, [D 2 ]-dichloromethane, 233 K): δ 19 F / δ 19 F = / (o-c 6 F a 5 / m-c 6 F a 5 ), / (o-c 6 F b 5 / m-c 6 F b 5 ), / (o -C 6 F a 5 / m -C 6 F a 5 ), / (o-c 6 F c 5 / m-c 6 F c 5, m -C 6 F c 5 ), / (o -C 6 F c 5 / m-c 6 F c 5, m -C 6 F c 5 ), / (o -C 6 F b 5 / m -C 6 F b 5 ), / 166.8, (p-c 6 F b 5 / m -C 6 F b 5, m-c 6 F b 5 ), / 169.8, (p-c 6 F a 5 / m-c 6 F a 5, m -C 6 F a 5 ), / (p-c 6 F c 5 / m/m -C 6 F c 5 ), / 136.1, (m -C 6 F b 5 / o -C 6 F b 5, p-c 6 F b 5 ), / 128.1, (m-c 6 F b 5 / o-c 6 F b 5, p-c 6 F b 5 ), / 132.2, 135.7, (m/m -C 6 F c 5 / o-c 6 F c 5, o -C 6 F c 5, p-c 6 F c 5 ), / 126.7, (m-c 6 F a 5 / o-c 6 F a 5, p-c 6 F a 5 ), / 130.6, (m -C 6 F a 5 / o -C 6 F a 5, p-c 6 F a 5 ). 1 H, 1 H GCOSY (500 MHz / 500 MHz, [D 2 ]-dichloromethane, 233 K): δ 1 H / δ 1 H = 8.39 / 7.66, 1.61 (o -Tol a / m -Tol a, o-tol CH3a ), 7.69 / 7.33, 1.61 (p-tol a / m-tol a, o-tol CH3a ), 7.66 / 8.39, 1.61 (m -Tol a / o -Tol a, o-tol CH3a ), 7.64 / 7.56, 7.33, 2.21 (p-tol c / m-tol c, m -Tol c, o-tol CH3c ), 7.56 / 7.64, 2.21 (m-tol c / p-tol c, o-tol CH3c ), 7.46 / 7.21, 1.87 (p-tol b / m-tol b, m -Tol b, o-tol CH3b ), 7.45 / 7.33, 2.21 (o -Tol c / m -Tol c, o-tol CH3c ), 7.33 / 7.69, 1.61 (m-tol a / p-tol a, o-tol CH3a ), 7.33 / 7.45, 2.21 (m -Tol c / o -Tol c, o-tol CH3c ), 7.33 / 7.21, 1.87 (o -Tol b / m -Tol b, o-tol CH3b ), 7.21 / 7.46, 7.33, 1.87 (m-tol b, m -Tol b / p-tol b, o -Tol b, o-tol CH3b ), 2.58 / 2.30, 0.46, 0.79 ( = CH [B] 2 / = CH 2 [B], CH 2 [B], CH [B] 2 ), 2.30 / 2.58, 0.46, 0.79 ( = CH 2 [B] / = CH [B] 2, CH 2 [B], CH [B] 2 ), 2.21 / 7.64, 7.56, 7.45, 7.33 (o-tol CH3c / p-tol c, m-tol c, o -Tol c, m -Tol c ), 1.87 / 7.46, 7.33, 7.21 (o-tol CH3b / p-tol b, o -Tol b, m-tol b, m -Tol b ), 1.67 / 1.56, 0.82, 0.69 ( CH [P] 2 / CH 2 [P], CH [P] 2, CH 2 [P] ), 1.61 / 8.39, 7.69, 7.66, 7.33 (o-tol CH3a / o -Tol a, p-tol a, m -Tol a, m-tol a ), 1.56 / 1.67, 0.82, 0.69 ( CH 2 [P] / CH [P] 2, CH [P] 2, CH 2 [P] ), 0.82 / 1.67, 1.56, 0.69, 0.39 (CH [P] 2 / CH [P] 2, CH 2 [P], CH 2 [P], CH [P] 3 ), 0.69 / 1.67, 1.56, 0.82, 0.39 (CH 2 [P] / CH [P] 2, CH 2 [P], CH [P] 2, CH [P] 3 ), 0.46 / 2.58, 2.30, 0.04, 0.79 (CH [B] 2 / = CH [B] 2, = CH 2 [B], CH [B] 3, CH [B] 2 ), 0.39 / 0.82, 0.69 (CH [P] 3 / CH [P] 2, CH 2 [P] ), 0.04 / 0.46, 0.79 (CH [B] 3 / CH 2 [B], CH [B] 2 ), 0.79 / 2.58, 2.30, 0.46, 0.04 (CH [B] 2 / = CH [B] 2, = CH 2 [B], CH 2 [B], CH [B] 3 ).

5 -S5- of 47 1 H, 13 C GHSQC (500 MHz / 125 MHz, [D 2 ]-dichloromethane, 233 K): δ 1 H / δ 13 C = 8.39 / (o -Tol a / o -Tol a ), 7.69 / (p-tol a / p-tol a ), 7.66 / (m -Tol a / m -Tol a ), 7.64 / 133.9, (p-tol c / p-tol c ), 7.56 / (m-tol c / m-tol c ), 7.46 / (p-tol b / p-tol b ), 7.45 / (o -Tol c / o -Tol c ), 7.33 / 134.4, 133.0, (m-tol a, o -Tol b, m -Tol c / o -Tol b, m-tol a, m -Tol c ), 7.21 / 132.6, (m-tol b, m -Tol b / m-tol b, m -Tol b ), 2.58 / 46.9 ( = CH [B] 2 / = CH [B] 2 ), 2.30 / 46.9 ( = CH 2 [B] / = CH [B] 2 ), 2.21 / 22.8 (o-tol CH3c / o-tol CH3c ), 1.87 / 23.1 (o-tol CH3b / o-tol CH3b ), 1.67 / 20.9 ( CH [P] 2 / CH [P] 2 ), 1.61 / 22.9 (o-tol CH3a / o-tol CH3a ), 1.56 / 20.9 ( CH 2 [P] / CH [P] 2 ), 0.82 / 20.8 (CH [P] 2 / CH [P] 2 ), 0.69 / 20.8 (CH 2 [P] / CH [P] 2 ), 0.46 / 21.5 (CH 2 [B] / CH [B] 2 ), 0.39 / 12.7 (CH [P] 3 / CH [P] 3 ), 0.04 / 15.1 (CH [B] 3 / CH [B] 3 ), 0.79 / 21.5 (CH [B] 2 / CH [B] 2 ). 1 H, 13 C GHMBC (500 MHz / 125 MHz, [D 2 ]-dichloromethane, 233 K): δ 1 H / δ 13 C = 8.39 / 143.3, (o -Tol a / o-tol a, p-tol a ), 7.69 / 143.3, 137.3, (p-tol a / o-tol a, o -Tol a, m-tol a ), 7.66 / 143.3, 137.3, 133.0, (m -Tol a / o-tol a, o -Tol a, m-tol a, i-tol a ), 7.64 / 145.0, 134.0, 127.4, (p-tol c / o-tol c, o -Tol c, m -Tol c, i-tol c ), 7.56 / 145.0, 127.4, 119.3, 22.8 (m-tol c / o-tol c, m -Tol c, i-tol c, o-tol CH3c ), 7.46 / 144.6, 133.5, 125.6, (p-tol b / o-tol b, p-tol b, m -Tol b, i-tol b ), 7.45 / 144.9, 133.9, 22.8 (o -Tol c / o-tol c, p-tol c, o-tol CH3c ), 7.33 / 144.7, 133.5, 133.1, 132.6, 127.1, 119.3, 118.3, 23.1, 22.9, 22.8 (m-tol a, o -Tol b, m -Tol c / o-tol b, p-tol b, m-tol c, m-tol b, m -Tol a, i-tol c, i-tol a, o-tol CH3b, o-tol CH3a, o-tol CH3c ), 7.21 / 144.7, 134.4, 133.5, 132.6, 125.6, 119.9, 23.1 (m-tol b, m -Tol b / o-tol b, o -Tol b, p-tol b, m -Tol b, m-tol b, i-tol b, o-tol CH3b ), 2.58 / ( = CH [B] 2 / =C P ), 2.21 / 144.9, 133.1, (o-tol CH3c / o-tol c, m-tol c, i-tol c ), 1.87 / 144.6, 132.6, (o-tol CH3b / o-tol b, m-tol b, i-tol b ), 1.67 / 78.7, 20.8, 12.7 ( CH [P] 2 / C C [P], CH 2, CH2 CH [P] 3 ), 1.61 / 143.3, 133.0, (o-tol CH3a / o-tol a, m-tol a, i-tol a ), 1.56 / 78.7, 20.8, 12.7 ( CH 2 [P] / C C, [P] CH 2, CH [P] 3 ), 0.82 / 99.6, 20.9, 12.7 (CH [P] 2 / C CH2, CH [P] 2, CH [P] 3 ), 0.69 / 99.6, 20.9, 12.7 (CH 2 [P] / C CH2, CH [P] 2, CH [P] 3 ), 0.39 / 20.9 (CH [P] 3 / CH [P] 2 ), 0.04 / 46.9, 21.5 (CH [B] 3 / = CH [B] 2, CH [B] 2 ). 1 H TOCSY (500 MHz, [D 2 ]-dichloromethane, 233 K): δ 1 H irr / δ 1 H res = 2.21 / 7.64, 7.56, 7.45, 7.33 (o-tol CH3c / p-tol c, m-tol c, o -Tol c, m -Tol c ), 1.87 / 7.46, 7.33, 7.21 (o-tol CH3b / p-tol b, o -Tol b, m-tol b, m -Tol b ), 1.61 / 8.39, 7.69, 7.66, 7.33 (o-tol CH3a / o -Tol a, p-tol a, m -Tol a, m-tol a ). 1 H, 1 H NOE (500 MHz, [D 2 ]-dichloromethane, 233 K): δ 1 H irr / δ 1 H res = 7.56 / 2.21 (m-tol c / o-tol CH3c ), 7.21 / 1.87 (m-tol b, m -Tol b / o-tol CH3b ), 7.33 / 1.61 (m-tol a / o-tol CH3a ).

6 -S6- of 47 1 H NMR (500 MHz, [D 2 ]-dichloromethane, 233 K) 13 C{ 1 H} NMR (125 MHz, [D 2 ]-dichloromethane, 233 K) 11 B{ 1 H} NMR (160 MHz, [D 2 ]-dichloromethane, 233 K)

7 -S7- of 47 (2) 31 P{ 1 H} NMR (202 MHz, [D 2 ]-dichloromethane, 233 K) (1) 31 P NMR (202 MHz, [D 2 ]-dichloromethane, 233 K) 19 F NMR (470 MHz, [D 2 ]-dichloromethane, 233 K)

8 -S8- of 47 1 H, 13 C GHSQC (500 MHz / 125 MHz, [D 2 ]-dichloromethane, 233 K) 19 F, 19 F GCOSY (470 MHz, [D 2 ]-dichloromethane, 233K)

9 -S9- of 47 X-ray crystal structure analysis of 5: formula C 49 H 35 BF 15 P, M = , colourless crystal, 0.30 x 0.15 x 0.10 mm, a = (7), b = (6), c = (5) Å, β = (2), V = (4) Å 3, ρ calc = gcm -3, µ = mm -1, empirical absorption correction (0.671 T 0.869), Z = 8, monoclinic, space group C2/c (No. 15), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.60 Å -1, 7808 independent (R int = 0.057) and 6738 observed reflections [I>2σ(I)], 600 refined parameters, R = 0.047, wr 2 = 0.120, max. (min.) residual electron density 0.37 (-0.48) e.å -3, hydrogen atoms calculated and refined as riding atoms. Compound trans-6 B(C 6 F 5 ) 3 (332.8 mg, mmol, 1.3 eq) and tri-tert-butylphosphane (131.5 mg, mmol, 1.3 eq) were dissolved in n-pentane (15 ml). In a second flask 4,6-decadiyne (174.4 mg, µl, mmol, 2 eq, excess) was dissolved in n-pentane (4 ml). The FLP solution was added to the diyne solution and stirred for six days. After 24 hours small crystals were formed. After six days the mixture was dried in vacuo to get a white solid (388 mg). This crude product was investigated by NMR spectroscopy and showed a second compound containing a phosphonium ion which could not be identified yet (trans-6 : unknown product = 3:1). Subsequently the crude product (336 mg) was purified by crystallization from dichloromethane/pentane (r.t.) to yield trans-6 as white crystals (235 mg, 42%). Crystals suitable for X-ray crystal structure analysis were obtained by diffusion method of a dichloromethane/pentane solution at 40 C. Anal. Calc. for C 40 H 41 BF 15 P: C 56.62, H 4.87; found: C 55.18, H IR (KBr): ~ υ = 3680 (w), 3416 (w), 3295 (w), 3027 (w), 2965 (m), 2931 (w), 2872 (m), 2814 (w), 2733 (w), 2545 (w), 2475 (w), 2385 (w), 2094 (w), 2015 (s), 1862 (w), 1643 (s), 1604

10 -S10- of 47 (w), 1519 (m), 1439 (m) 1371 (m), 1273 (s), 1168 (s), 1086 (s), 1026 (m). 984 (s), 932 (m), 894 (m), 836 (w), 802 (s). M. p.: 227 C (DSC). HRMS calc. for C 40 H 41 BF 15 PNa + : ; found: [B] (C 6 F 5 ) 3 B P t Bu 3 [P] 1 H NMR (600 MHz, [D 2 ]-dichloromethane, 298 K): δ = 2.47 (m, 2H, = CH [B] 2 ), 2.14 (m, 2H, = CH [P] 2 ), 1.67 (d, 3 J PH = 13.8 Hz, 27H, t Bu), 1.09 (m, 2H, CH [P] 2 ), 0.89 (m, 2H, CH [B] 2 ), 0.69 (t, 3 J HH = 7.3 Hz, 3H, CH [B] 3 ), 0.68 (t, 3 J HH = 7.3 Hz, 3H, CH [P] 3 ). 13 C{ 1 H} NMR (150 MHz, [D 2 ]-dichloromethane, 298 K): δ = (br m, =C= P ), (br, =C B ), (dm, J = 15.1 Hz, =C= B ), 84.6 (d, 1 J PC = 71.4 Hz, =C P ), 41.9 (d, 1 J PC = 29.6 Hz, t Bu), 40.7 (dm, J = 5.1 Hz, = CH [B] 2 ), 38.5 (d, 2 J PC = 7.7 Hz, = CH [P] 2 ), 31.3 ( t Bu), 26.5 (m, CH [B] 2 ), 23.8 (d, 3 J PC = 3.1 Hz, CH [P] 2 ), 14.7 (CH [B] 3 ), 13.5 (d, 4 J PC = 0.5 Hz, CH [P] 3 ), [C 6 F 5 not listed]. 31 P{ 1 H} NMR (242 MHz, [D 2 ]-dichloromethane, 298 K): δ = 45.6 (m). 31 P NMR (121 MHz, [D 2 ]-dichloromethane, 297 K): δ = 45.6 (m, ν 1/2 95 Hz). 11 B{ 1 H} NMR (96 MHz, [D 2 ]-dichloromethane, 298 K): δ = 12.7 (ν 1/2 20 Hz). 19 F NMR (564 MHz, [D 2 ]-dichloromethane, 295 K): δ = (m, 2F, o-c 6 F 5 ), (m, 1F, p-c 6 F 5 ), (m, 2F, m-c 6 F 5 ), [ δ 19 F m,p = 4.1]. 1 H, 1 H GCOSY (600 MHz / 600 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H / δ 1 H = 2.47 / 0.89 ( = CH [B] 2 / CH [B] 2 ), 2.14 / 1.09 ( = CH [P] 2 / CH [P] 2 ), 1.09 / 2.14, 0.68 (CH [P] 2 / = CH [P] 2, CH [P] 3 ), 0.89 / 2.47, 0.69 (CH [B] 2 / = CH [B] 2, CH [B] 3 ), 0.69 / 0.89 (CH [B] 3 / CH [B] 2 ), 0.68 / 1.09 (CH [P] 3 / CH [P] 2 ). 1 H, 13 C GHSQC (600 MHz / 150 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H / δ 13 C = 2.47 / 40.7 ( = CH [B] 2 ), 2.14 / 38.5 ( = CH [P] 2 ), 1.67 / 31.3 ( t Bu), 1.09 / 23.8 (CH [P] 2 ), 0.89 / 26.5 (CH [B] 2 ), 0.69 / 14.7 (CH [B] 3 ), 0.68 / 13.5 (CH [P] 3 ). 1 H, 13 C GHMBC (600 MHz / 150 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H / δ 13 C = 2.14 / 187.5, 84.6, 23.8, 13.5 ( = CH [P] 2 / =C= P, =C P, CH [P] 2, CH [P] 3 ), 1.67 / 42.1, 31.3 ( t Bu / t Bu, t Bu), 1.09 / 84.6, 38.5, 13.5 (CH [P] 2 / =C P, = CH [P] 2, CH [P] 3 ), 0.89 / 40.7, 14.7 (CH [B] 2 / = CH [B] 2, CH [B] 3 ), 0.69 / 40.7, 26.5 (CH [B] 3 / = CH [B] 2, CH [B] 2 ), 0.68 / 38.5, 23.8 (CH [P] 3 / = CH [P] 2, CH [P] 2 ). 1 H TOCSY (500 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H irr / δ 1 H res = 2.47 / 0.89, 0.69 ( = CH [B] 2 / CH [B] 2, CH [B] 3 ), 2.14 / 1.09, 0.68 ( = CH [P] 2 / CH [P] 2, CH [P] 3 ), 1.09 / 2.14, 0.68 (CH [P] 2 / = CH [P] 2, CH [P] 3 ), 0.89 / 2.47, 0.69 (CH [B] 2 / = CH [B] 2, CH [B] 3 ).

11 -S11- of 47 1 H NMR (500 MHz, [D 2 ]-dichloromethane, 298 K) 13 C{ 1 H} NMR (150.8 MHz, [D 2 ]-dichloromethane, 298 K) 11 B{ 1 H} NMR (96 MHz, [D 2 ]-dichloromethane, 298 K)

12 -S12- of 47 (2) 31 P{ 1 H} NMR (242 MHz, [D 2 ]-dichloromethane, 298 K) (1) 31 P NMR (121 MHz, [D 2 ]-dichloromethane, 298 K) 19 F NMR (564 MHz, [D 2 ]-dichloromethane, 298 K)

13 -S13- of 47 1 H, 13 C GHMBC (600 MHz / 150 MHz, [D 2 ]-dichloromethane, 298 K) X-ray crystal structure analysis of trans-6: formula C 40 H 41 BF 15 P, M = , colourless crystal, 0.30 x 0.30 x 0.20 mm, a = (5), b = (4), c = (6) Å, α = (2), β = (2), γ = (2), V = (13) Å 3, ρ calc = gcm -3, µ = mm -1, empirical absorption correction (0.664 T 0.755), Z = 2, triclinic, space group P1 (No. 2), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.60 Å -1, 7099 independent (R int = 0.042) and 6401 observed reflections [I>2σ(I)], 539 refined parameters, R = 0.043, wr 2 = 0.121, max. (min.) residual electron density 0.32 (-0.26) e.å -3, hydrogen atoms calculated and refined as riding atoms.

14 -S14- of 47 NMR spectra of the crude product 1 H NMR (500 MHz, [D 2 ]-dichloromethane, 298 K) F NMR (470 MHz, [D 2 ]-dichloromethane, 298 K)

15 -S15- of 47 (2) 31 P NMR (202 MHz, [D 2 ]-dichloromethane, 298 K) (1) 31 P{ 1 H} NMR (202 MHz, [D 2 ]-dichloromethane, 298 K) 11 B{ 1 H} NMR (96 MHz, [D 2 ]-dichloromethane, 298 K) Compound cis-6 The cumulene trans-6 (10 mg, 0.01 mmol) was dissolved in deuterated dichloromethane and irradiated with UV-light (Philips HPK 125 lamp) for 20 minutes to give a photostationary equilibrium of cis and trans isomers in a ratio of 0.9:1 (by 1 H NMR). Crystals suitable for X-ray crystal structure analysis were obtained by diffusion-method of the reaction mixture with dichloromethane/pentane at 40 C. [B] [P] 1 H NMR (500 MHz, [D 2 ]-dichloromethane, 298 K): δ = 2.45 (br, 2H, = CH [B] 2 ), 2.37 (m, 2H, = CH [P] 2 ), 1.69 (m, CH [P] 2 ), 1.54 (d, 3 J PH = 13.9 Hz, 27H, (C 6 F 5 ) 3 B P t Bu 3 t Bu), 1.17 (br, 2H, CH 2 [B] ), 0.95 (t, 3 J HH = 7.3 Hz, 3H, CH 3 [P] ), 0.74 (t, 3 J HH = 7.4 Hz, 3H, CH 3 [B] ), [[P] and [B] tentative assigned].

16 -S16- of C{ 1 H} NMR (150 MHz, [D 2 ]-dichloromethane, 298 K): δ = 42.8 (br m, = CH [B] 2 ), 41.6 (d, 2 J PC = 29.7 Hz, t Bu), 40.5 (d, 3 J PC = 8.6 Hz, = CH [P] 2 ), 31.0 (s, t Bu), 25.3 (br, CH [B] 2 ), 24.7 (d, 3 J PC = 2.8 Hz, CH [P] 2 ), 14.3 (CH [B] 3 ), 13.7 (CH [P] 3 ), n.o. (=C B, =C=, =C P ), [C 6 F 5 not listed]. 31 P{ 1 H} NMR (202 MHz, [D 2 ]-dichloromethane, 298 K): δ = 45.7 (m). 11 B{ 1 H} NMR (160 MHz, [D 2 ]-dichloromethane, 298 K): δ = 13.5 (ν 1/2 20 Hz). 19 F NMR (470 MHz, [D 2 ]-dichloromethane, 298 K): δ = (br, 2F, o-c 6 F 5 ), (m, 1F, p-c 6 F 5 ), (br, 2F, m-c 6 F 5 ), [ δ 19 F m,p = 3.7]. 19 F, 19 F GCOSY (470 MHz / 470 MHz, [D 2 ]-dichloromethane, 298 K): δ 19 F / δ 19 F = / (o-c 6 F 5 / m-c 6 F 5 ), / (p-c 6 F 5 / m-c 6 F 5 ), / 131.3, (m-c 6 F 5 / o-c 6 F 5, p-c 6 F 5 ) 1 H, 1 H GCOSY (600 MHz / 600 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H / δ 1 H = 2.45 / 1.17 ( = CH [B] 2 / CH [B] 2 ), 2.37 / 1.69 ( = CH [P] 2 / CH [P] 2 ), 1.69 / 2.37, 0.95 (CH [P] 2 / = CH [P] 2, CH [P] 3 ), 1.17 / 2.45, 0.74 (CH [B] 2 / = CH [B] 2, CH [B] 3 ), 0.95 / 1.69 (CH [P] 3 / CH [P] 2 ), 0.74 / 1.17 (CH [B] 3 / CH [B] 2 ). 1 H, 13 C GHSQC (500 MHz / 125 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H / δ 13 C = 2.45 / 42.8 ( = CH [B] 2 ), 2.37 / 40.5 ( = CH [P] 2 ), 1.69 / 24.7 (CH [P] 2 ), 1.54 / 31.0 ( t Bu), 1.17 / 25.3 (CH [B] 2 ), 0.95 / 13.7 (CH [P] 3 ), 0.74 / 13.5 (CH [B] 3 ). 1 H, 13 C GHMBC (500 MHz / 125 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H / δ 13 C = 2.37 / 24.7 ( = CH [P] 2 / CH [P] 2 ), 1.54 / 41.5 ( t Bu / t Bu), 0.95 / 40.5, 24.7 (CH [P] 3 / = CH [P] 2, CH [P] 2 ), 0.74 / 42.8, 25.3 (CH [B] 3 / = CH [B] 2, CH [B] 2 ). 1 H TOCSY (500 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H irr / δ 1 H res = 2.37 / 1.69, 0.95 ( = CH [P] 2 / CH [P] 2, CH [P] 3 ), 1.69 / 2.37, 0.95 (CH [P] 2 / = CH [P] 2, CH [P] 3 ), 1.17 / 2.45, 0.74 (CH [B] 2 / = CH [B] 2, CH [B] 3 ), 0.95 / 2.37, 1.69 (CH [P] 3 / = CH [P] 2, CH [P] 2 ), 0.74 / 2.45, 1.17 (CH [B] 3 / = CH [B] 2, CH [B] 2 ). 1 H NMR (500 MHz, [D 2 ]-dichloromethane, 298 K)

17 -S17- of C{ 1 H} NMR (125.7 MHz, [D 2 ]-dichloromethane, 298 K) 31 P{ 1 H} NMR (202 MHz, [D 2 ]-dichloromethane, 298 K) [c: cis, t: trans] 11 B{ 1 H} NMR (160 MHz, [D 2 ]-dichloromethane, 298 K) [c: cis, t: trans]

18 -S18- of F NMR (470 MHz, [D 2 ]-dichloromethane, 298 K) 1 H, 1 H GCOSY (600 MHz / 600 MHz, [D 2 ]-dichloromethane, 298 K) X-ray crystal structure analysis of cis-6: formula C 40 H 41 BF 15 P * 1,5 CH 2 Cl 2, M = colourless crystal, 0.30 x 0.28 x 0.13 mm, a = (3), b = (8), c = (13) Å, α = (3), β = (2), γ = (3), V = (4) Å 3, ρ calc = gcm -3, µ = mm -1, empirical absorption correction (0.458 T 0.690), Z = 4, triclinic, space group P1 (No. 2), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.60 Å -1, independent (R int = 0.062) and observed reflections

19 -S19- of 47 [I>2σ(I)], 1131 refined parameters, R = 0.066, wr 2 = 0.187, max. (min.) residual electron density 1.08 (-0.68) e.å -3, hydrogen atoms calculated and refined as riding atoms. Compound 7 B(C 6 F 5 ) 3 (256 mg, mmol, 1 eq) and tri-tert-butylphosphane (101.1 mg, mmol, 1 eq) were dissolved in n-pentane (10 ml). In a second flask 2,4-hexadiyne (39.1 mg, mmol, 1 eq) was dissolved in n-pentane (6 ml). The obtained FLP-solution was added to the diyne solution and the obtained reaction mixture was stirred at room temperature for three days. After that time small crystals could obtain from that solution. The supernatant was decanted and the light orange solid (156 mg) was dried in vacuo. After additional five days at room temperature small crystals were observed in the supernatant. The solution was again decanted and the solid was dried in vacuo to yield a light orange solid (112 mg). Both solids were mixture of 7 and 8 (1,2- and 1,4-addition product) in a ratio of 4:1( 31 P NMR). The combined crude products (268 mg) were purified by crystallization (dichloromethane / pentane, 40 C) to get a white solid (48%, 194 mg). Crystals suitable for X- ray crystal structure analyses of both products were obtained by diffusion-method of a dichloromethane/pentane solution at 40 C. IR (KBr): ~ υ = 2917 (w), 1642 (w), 1514 (m), 1452 (m), 1378 (w), 1270 (w), 1159 (w), 1082 (m), 974 (m), 878 (w), 794 (w). HRMS calc. for C 36 H 33 BF 15 PNa + : ; found: H 3 C P t Bu : 1 H NMR (500 MHz, [D 2 ]-dichloromethane, 298 K): δ = 2.47 (m, 3H, = CH 3 ), 1.67 (C 6 F 5 ) 3 B (d, 3 J PH = 14.2 Hz, 27H, t Bu), 1.52 (d, J = 3.8 Hz, 3H, CH 3 ). CH 3 13 C{ 1 H} NMR (126 MHz, [D 2 ]-dichloromethane, 298 K): δ = (br 1:1:1:1 q,

20 -S20- of 47 1 J CB 55 Hz, =C B ), (dm, 1 J PC = 52.1 Hz, =C P ), 96.6 (d, 3 J PC = 9.9 Hz, C CH3 ), 83.7 (br d, 2 J PC 17 Hz, C), 44.3 (d, 1 J PC = 23.7 Hz, t Bu), 33.0 ( t Bu) 32.3 (m, = CH 3 ), 4.9 (d, J = 7.3 Hz, CH 3 ), [C 6 F 5 not listed]. 31 P NMR (202 MHz, [D 2 ]-dichloromethane, 298 K): δ = 59.3 (br m). 31 P{H} NMR (202 MHz, [D 2 ]-dichloromethane, 298 K): δ = 59.3 (m). 11 B{ 1 H} NMR (160 MHz, [D 2 ]-dichloromethane, 298 K): δ = 12.2 (ν 1/2 30 Hz). 19 F NMR (470 MHz, [D 2 ]-dichloromethane, 298 K): δ = (o), (o ), (t, 3 J FF = 20.5 Hz, 1F, p), (m ), (m) (each m, each 1F, C 6 F a 5 ), [ δ 19 F m,p = 3.7; 4.4]; (o), (o ), (p), (m), (m ) (each m, each 1F, C 6 F b 5 ), [ δ 19 F m,p = 4.2; 5.0]; (o), (o ), (p), (m ), (m) (each m, each 1F, C 6 F c 5 ), [ δ 19 F m,p = 4.6; 5.3]. 19 F, 19 F GCOSY (470 MHz / 470 MHz, [D 2 ]-dichloromethane, 298 K): δ 19 F / δ 19 F = / 132.9, 165.8, (o-c 6 F a 5 / o -C 6 F b 5, m-c 6 F a 5, m -C 6 F a 5 ), / 134.1, 168.2, (o-c 6 F c 5 / o -C 6 F a 5, m-c 6 F c 5, m -C 6 F c,b 5 ), / 130.9, (o-c 6 F b 5 / o -C 6 F c 5, m-c 6 F c,b 5 ), / 130.1, 168.2, (o-c 6 F c 5 / o-c 6 F b 5, m-c 6 F c 5, m -C 6 F c 5 ), / 127.0, 168.2, (o-c 6 F b 5 / o-c 6 F a 5, m-c 6 F c 5, m -C 6 F c,b 5 ), / 127.3, 130.1, 165.8, (o-c 6 F a 5 / o-c 6 F c 5, o-c 6 F b 5, m-c 6 F a 5, m-c 6 F a 5 ), / 165.8, (p-c 6 F a 5 / m-c 6 F a 5, m-c 6 F a 5 ), / 168.2, (p-c 6 F c 5 / m-c 6 F c 5, m-c 6 F c,b 5 ), / 168.0, (p-c 6 F b 5 / m-c 6 F b 5, m-c 6 F c,b 5 ), / 127.0, 134.1, 162.1, (m-c 6 F a 5 / o-c 6 F a 5, o-c 6 F a 5, p-c 6 F a 5, m-c 6 F a 5 ), / 127.0, 134.1, (m-c 6 F a 5 / o-c 6 F a 5, o-c 6 F a 5, p-c 6 F a 5 ), / 132.9, (m-c 6 F b 5 / o-c 6 F b 5, p-c 6 F b 5 ), / 127.3, 130.9, (m-c 6 F c 5 / o-c 6 F c 5, o-c 6 F c 5, p-c 6 F c 5 ), / 127.3, 130.1, 130.9, 132.9, 163.8, (m-c 6 F c,b 5 / o-c 6 F c 5, o-c 6 F b 5, o-c 6 F c 5, o-c 6 F b 5, p-c 6 F b 5, p-c 6 F c 5 ). 1 H, 1 H GCOSY (600 MHz / 600 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H / δ 1 H = 2.47 / 1.52 ( = CH 3 / CH 3 ), 1.52 / 2.47 ( CH 3 / = CH 3 ). 1 H, 13 C GHSQC (600 MHz / 150 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H / δ 13 C = 2.47 / 32.2 ( = CH 3 ), 1.67 / 32.9 ( t Bu), 1.52 / 4.89 ( CH 3 ). 1 H, 13 C GHMBC (600 MHz / 150 MHz, [D 2 ]-dichloromethane, 298 K): δ ( 1 H) / δ ( 13 C) = 2.47 / 199.4, ( = CH 3 / =C B, =C P ) 1.67 / 44.3 ( t Bu / t Bu), 1.52 / 105.8, 96.6, 83.7 ( CH 3 / =C P, C CH3, C).

21 -S21- of 47 Compound 8: [B] H 3 C P t Bu 3 1 H NMR (500 MHz, [D 2 ]-dichloromethane, 298 K): δ = 1.97 (d, 3 J PH = 9.6 Hz, 3H, CH 3 [P] ), 1.96 (br, 3H, CH 3 [B] ), 1.66 (d, 3 J PH = 13.9 Hz, 27H, t Bu). 13 C{ 1 H} NMR (150 MHz, 298 K, [D 2 ]-dichloromethane): δ = (=C= P ) 1, (C (s, =C= B ) 1, 79.1 (d, 1 J PC ~ 80 Hz, =C P ) 1, 41.9 (d, 1 J PC = 29.8 Hz, t 6 F 5 ) 3 B CH 3 Bu), 31.2 [P] (s, t Bu), 26.0 (m, 2 J PC = 8.8 Hz, CH [P] 3 ), 22.1 (m, CH [B] 3 ), n.o. (=C B ), [C 6 F 5 not listed. 1 from ghmbc experiment]. 31 P NMR (202 MHz, [D 2 ]-dichloromethane, 298 K): δ = 45.8 (m). 31 P{ 1 H} NMR (202 MHz, [D 2 ]-dichloromethane, 298 K): δ = 45.8 (m). 11 B{ 1 H} NMR (160 MHz, [D 2 ]-dichloromethane, 298 K): δ = 12.8 (ν 1/2 20 Hz). 19 F NMR (470 MHz, [D 2 ]-dichloromethane, 298 K): δ = (m, 2F, o-c 6 F 5 ), (t, 3 J FF = 20.4 Hz, 1F, p-c 6 F 5 ), (m, 2F, m-c 6 F 5 ) [ 19 F m,p = 4.1]. 19 F, 19 F GCOSY (470 MHz / 470 MHz, [D 2 ]-dichloromethane, 298 K): δ 19 F / δ 19 F = / (o-c 6 F 5 / m-c 6 F 5 ), / (p-c 6 F 5 / m-c 6 F 5 ), / 131.1, (m-c 6 F 5 / o-c 6 F 5, p-c 6 F 5 ). 1 H, 13 C GHSQC (600 MHz / 150 MHz, [D 2 ]-dichloromethane, 298 K): δ 1 H / δ 13 C = 2.06 / 24.9 (CH [B] 3 ), 1.96 / 22.1 (CH [P] 3 ), 1.66 / 31.2 ( t Bu). 1 H, 13 C GHMBC (600 MHz / 150 MHz, [D 2 ]-dichloromethane, 298 K): δ ( 1 H) / δ ( 13 C) = 1.96 / 187.2, 152.7, 78.5 (CH [P] 3 / =C= P, =C= B, =C P ), 1.66 / 41.9 ( t Bu CH3 3 / t Bu). 1 H NMR (500 MHz, [D 2 ]-dichloromethane, 298 K)

22 -S22- of C{ 1 H} NMR (125 MHz, [D 2 ]-dichloromethane, 298 K) 31 P NMR (202 MH, [D 2 ]-dichloromethane z, 298 K) 31 P{ 1 H} NMR (202 MHz, [D 2 ]-dichloromethane, 298 K)

23 -S23- of B{ 1 H} NMR (160 MHz, [D 2 ]-dichloromethane, 298 K) 19 F NMR (470 MHz, [D 2 ]-dichloromethane, 298 K) X-ray crystal structure analysis of 7: formula C 36 H 33 BF 15 P, M = , colourless crystal, 0.23 x 0.05 x 0.03 mm, a = (4), b = (3), c = (3) Å, β = (1), V = (13) Å 3, ρ calc = gcm - 3, µ = mm -1, empirical absorption correction (0.958 T 0.994), Z = 4, monoclinic, space group P2 1 /c (No. 14), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.59 Å -1, 5964 independent (R int = 0.043) and 4637 observed reflections [I>2σ(I)], 460 refined parameters, R = 0.077, wr 2 = 0.177, max. (min.) residual electron density 0.37 (-0.26) e.å -3, hydrogen atoms calculated and refined as riding atoms.

24 -S24- of 47 X-ray crystal structure analysis of 8: formula C 36 H 33 BF 15 P, M = , colourless crystal, 0.15 x 0.12 x 0.07 mm, a = (5), b = (4), c = (6) Å, β = (3), V = (2) Å 3, ρ calc = gcm -3, µ = mm -1, empirical absorption correction (0.791 T 0.894), Z = 4, monoclinic, space group P2 1 /c (No. 14), λ = Å, T = 223(2) K, ω and φ scans, reflections collected (±h, ±k, ±l), [(sinθ)/λ] = 0.60 Å -1, 6202 independent (R int = 0.042) and 5201 observed reflections [I>2σ(I)], 489 refined parameters, R = 0.045, wr 2 = 0.118, max. (min.) residual electron density 0.27 (-0.24) e.å -3, hydrogen atoms calculated and refined as riding atoms.

25 -S25- of 47 Compound 9 Compound 8 (20 mg) was dissolved in deuterated bromobenzene and filled in an NMR tube. The NMR tube was sealed and the clear reaction solution was heated for 5 hours at 80 C. During heating small crystals grew at the wall of the NMR tube (yield >90% (due to 1 H NMR experiment)). A few of these crystals were collected and used for X-ray crystal structure analysis. The rest of the solution mixture was dried in vacuo to yield a white solid. For low temperature NMR experiments the solid was dissolved again in deuterated dichloromethane. IR (KBr): ~ υ = 3826 (w), 3395 (w), 3225 (m), 2987 (m), 2911 (w), 2874 (w), 2735 (w), 2622 (w), 2477 (w), 2439 (w), 2386 (w), 2214 (w), 2174 (w), 2041 (m), 1918 (w), 1643 (s), 1600 (w), 1522 (m), 1439 (m), 1378 (m), 1341 (w), 1274 (s), 1179 (m), 1092 (s), 1032 (m), 984 (m), 935 (w), 886 (s), 860 (m), 800 (s). M. p. 227 C (DSC). HMRS: calc. for C 32 H 25 BF 15 PNa + : ; found: H NMR (600 MHz, [D 2 ]-dichloromethane, 273 K): δ = 5.86 (d, 1 J PH = Hz, H 3 C (C 6 F 5 ) 3 B PH t Bu 2 PH), 2.02 (s, 3H, = CH 3 ), 1.64 (d, J = 4.8 Hz, 3H, CH 3 ), 1.57 (d, 3 J PH = 16.9 Hz, 9H, t Bu ), 1.32 (d, 3 J PH = 16.9 Hz, 9H, t Bu). 13 C{ 1 H} NMR (150 MHz, 273 K, [D 2 ]-dichloromethane): δ = 97.1 (dm, CH 3 1 J PC 69 Hz, =C P ), 96.4 (d, 3 J PC = 8.7 Hz, C CH3 ), 77.3 (m, C), 35.7 (d, 1 J PC = 35.3 Hz, t Bu ), 35.5 (d, 1 J PC = 35.5 Hz, t Bu), 28.0 (CH tbu 3 ), 27.9 (CH tbu 3 ), 24.8 (br, = CH 3 ), 4.1 (d, J = 2.0 Hz, CH 3 ), n.o. (=C B ), [C 6 F 5 not listed]. 31 P NMR (242 MHz, [D 2 ]-dichloromethane, 273 K): δ = 21.4 (br d, 1 J PH 431 Hz). 31 P{ 1 H} NMR (242 MHz, [D 2 ]-dichloromethane, 273 K): δ = 21.4 (m). 11 B{ 1 H} NMR (192 MHz, [D 2 ]-dichloromethane, 273 K): δ = 13.2 (ν 1/2 30 Hz). 19 F NMR (564 MHz, 273 K, [D 2 ]-dichloromethane): δ = (o), (o ), (t, 3 J FF = 20.6 Hz, 1F, p), (m ), (m) (each m, each 1F, C 6 F a 5 ), [ δ 19 F m,p = 4.5; 5.1]; (o), (o ), (t, 3 J FF = 21.1 Hz, 1F, p), (m ), (m) (each m, each 1F, C 6 F b 5 ), [ δ 19 F m,p = 3.9; 4.0]; (o), (o ), (t, 3 J FF = 20.6 Hz, 1F, p), (m ), (m) (each m, each 1F, C 6 F c 5 ), [ δ 19 F m,p = 3.8; 5.0]. 19 F, 19 F GCOSY (564 MHz / 564 MHz, [D 2 ]-dichloromethane, 273 K): δ 19 F / δ 19 F = / 132.4, (o C 6 F a 5 / o C 6 F c 5, m C 6 F a 5 ), / (o C 6 F c 5 / m C 6 F c 5 ), / (o C 6 F b 5 / m C 6 F b 5 ), / (o C 6 F a 5 / m C 6 F a 5 ), / (o C 6 F b 5 / m C 6 F b 5 ), / 128.4, (o C 6 F c 5 / o C 6 F a 5, m C 6 F a 5 ), / 166.0, (p C 6 F b 5 / m C 6 F b 5, m C 6 F b 5 ), / 166.8, (p C 6 F a 5 / m C 6 F a 5, m C 6 F a 5 ), / 167.0, (p C 6 F c 5 / m C 6 F c 5, m C 6 F c 5 ), / 132.3, (m C 6 F b 5 / o C 6 F b 5, p C 6 F b 5 ), / 130.9, (p C 6 F b 5 / o C 6 F b 5, p C 6 F p 5 ),

26 -S26- of / 131.9, (m C 6 F a 5 / o C 6 F a 5, p C 6 F a 5 ), / 132.4, (m C 6 F c 5 / o C 6 F c 5, p C 6 F c 5 ), / 128.4, 131.9, (m C 6 F a 5 / o C 6 F a 5, o C 6 F a 5, p C 6 F a 5 ), / 130.7, (m C 6 F c 5 / o C 6 F c 5, p C 6 F c 5 ). 1 H, 1 H GCOSY (600 MHz / 600 MHz, [D 2 ]-dichloromethane, 273 K): δ 1 H / δ 1 H = 5.86 / 1.64, 1.57, 1.32 (PH / CH 3, t Bu, t Bu ), 2.02 / 1.64 ( = CH 3 / CH 3 ), 1.64 / 5.86, 2.02 ( CH 3 / PH, = CH 3 ), 1.57 / 5.86, 1.32 ( t Bu / PH, t Bu ), 1.32 / 5.86, 1.57 ( t Bu / PH, t Bu). 1 H, 13 C GHSQC (600 MHz / 150 MHz, [D 2 ]-dichloromethane, 273 K): δ 1 H / δ 13 C = 2.02 / 24.7 ( = CH 3 ), 1.64 / 4.1 ( CH 3 ), 1.57 / 28.0 (CH tbu 3 ), 1.32 / 27.8 (CH tbu 3 ). 1 H, 13 C GHMBC (600 MHz / 150 MHz, [D 2 ]-dichloromethane, 273 K): δ ( 1 H) / δ ( 13 C) = 5.86 / 97.1, 77.3, 35.7, 35.4, 28.0, 27.8 (PH / =C P, C, t Bu, t Bu, CH tbu 3, CH tbu 3 ), 2.02 / 97.1, 77.3 ( = CH 3 / =C P, C), 1.64 / 96.4, 77.3 ( CH 3 / C CH3, C), 1.57 / 122.4, 35.7, 35.4, 27.8 ( t Bu / n.a., t Bu, t Bu, CH tbu 3 ), 1.32 / 122.4, 35.7, 35.4, 28.0 ( t Bu / n.a., t Bu, t Bu, CH tbu 3 ). 1 H NMR (600 MHz, 273 K, [D 2 ]-dichloromethane) 13 C{ 1 H} NMR (150 MHz, [D 2 ]-dichloromethane, 273 K)

27 -S27- of 47 (2) 31 P NMR (242 MHz, [D 2 ]-dichloromethane, 273 K) (1) 31 P{ 1 H} NMR (242 MHz, [D 2 ]-dichloromethane, 273 K) 11 B{ 1 H} NMR (192 MHz, [D 2 ]-dichloromethane, 273 K) 19 F NMR (564 MHz, [D 2 ]-dichloromethane, 273 K)

28 -S28- of F, 19 F GCOSY (564 MHz / 564 MHz, [D 2 ]-dichloromethane, 273 K) X-ray crystal structure analysis of 9: formula C 32 H 25 BF 15 P, M = , colourless crystal, 0.50 x 0.25 x 0.02 mm, a = (5), b = (4), c = (4) Å, β = (3), V = (16) Å 3, ρ calc = gcm - 3, µ = mm -1, empirical absorption correction (0.463 T 0.964), 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), [(sinθ)/λ] = 0.60 Å -1, 5435 independent (R int = 0.050) and 4795 observed reflections, space group [I>2σ(I)], 453 refined parameters, R = 0.040, wr 2 = 0.107, max. (min.) residual electron density 0.22 (-0.27) e.å -3, hydrogen atoms calculated and refined as riding atoms.

29 -S29- of 47 DFT calculations Coordinates of the calculated structures in TURBOMOLE format (bohrs): a) gasphase geometries diin1 (R=IP) c c c c c c c c c c h h h h h h h h h h h h h h diin2 (R=Me) c c c c c c h h h h h h FLP 4b p b h c c c c

30 -S30- of c c c c c c c c c c c c c c c c c c c c c c c c c c f f f f f f f f f f f f f f f h h h h h h h h h h h h h h

31 -S31- of h h h h h h h h h h h h 6-cis p b c c c c c h h c h h c h h h c h h c h h c h h h c c h h h c h h h c h h h c c

32 -S32- of h h h c h h h c h h h c c h h h c h h h c h h h c c f c f c f c f c f c c f c f c f c f c f c c f c f c f c f

33 -S33- of c f 6-trans p b c c c c c h h c h h c h h h c h h c h h c h h h c c h h h c h h h c h h h c c h h h c h h h c h h