Thomas Özgün, Guo-Qiang Chen, Constantin G. Daniliuc ... · The reaction mixture was warmed to r....

S1

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, 48149 Münster,

Germany

† Department of Chemistry, Georgetown University, Box 571227, Washington, D.C. 20057-1227, United States ‡ Institut für Physikalische Chemie, Westfälische Wilhelms-Universität, Corrensstrasse 30, 48149 Münster, Germany

Supporting Information

S2

Table of contents

1 General Procedures ............................................................................................................. 3

2 Experimental Part ................................................................................................................ 5

2.1 Synthesis of compounds .............................................................................................. 5

Synthesis of compound 9 .................................................................................................... 5

Synthesis of compound 10a ................................................................................................ 7

Synthesis of compound 10b .............................................................................................. 12

Synthesis of compound 11 ................................................................................................ 18




Generation of compound 14-D2 ........................................................................................ 40







3 Solid State NMR Data ........................................................................................................ 65

4 EPR Data ............................................................................................................................ 69

S3

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 (1H: 500 MHz, 13C: 126 MHz, 19F: 470 MHz, 11B: 160 MHz, 31P: 202 MHz) and on an

Agilent DD2- 600 MHz (1H: 600 MHz, 13C: 151 MHz, 19F: 564 MHz, 11B: 192 MHz, 31P: 243

MHz). 1H NMR and 13C NMR: chemical shifts are given relative to TMS and referenced to the

solvent signal. 19F NMR: chemical shifts are given relative to CFCl3 (δ = 0, external reference),

11B NMR: chemical shifts are given relative to BF3∙Et2O (δ = 0, external reference), 31P NMR:

chemical shifts are given relative to H3PO4 (85% in D2O) (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, 307-326); absorption correction, Denzo

(Z. Otwinowski, D. Borek, W. Majewski, W. Minor, Acta Crystallogr. 2003, A59, 228-234);

structure solution SHELXS-97 (G. M. Sheldrick, Acta Crystallogr. 1990, A46, 467-473);

structure refinement SHELXL-97 (G. M. Sheldrick, Acta Crystallogr. 2008, A64, 112-122) 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 V2014.5-0 (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 wR2 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.

S4

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, 6992-6994; Parks, D. J.; Piers, W. E.; Yap, G. P. A.

Organometallics, 1998, 17, 5492-5503.] were prepared according to the literature.

S5

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, 765-769.

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: CH2Cl2:CyH = 15:85; Rf: 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 C26H31P: C: 83.39; H: 8.34. Found: C: 83.20; H: 8.43.

1H NMR (500 MHz, dichloromethane-d2, 299 K): δ 6.81 (dm, 4JPH = 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-CH2), 2.09 (m, 2H, 3-

CH2), 1.62 (m, 2H, 5-CH2), 1.57 (m, 2H, 4-CH2).

13C{1H} NMR (126 MHz, dichloromethane-d2, 299 K): δ 142.2 (d, 2JPC = 15.6 Hz, o-Mes), 138.7

(p-Mes), 135.6 (d, 4JPC = 2.6 Hz, 2-CH), 130.5 (d, 1JPC = 12.6 Hz, i-Mes), 130.2 (d, 3JPC =

3.6 Hz, m-Mes), 121.7 (d, 3JPC = 1.5 Hz, 1-C=), 109.2 (d, 2JPC = 8.8 Hz, ≡C), 84.3 (d, 1JPC =

3.4 Hz, PC≡), 28.8 (d, 4JPC = 1.6 Hz, 6-CH2), 26.1 (3-CH2), 23.0 (d, 3JPC = 14.4 Hz, o-CH3Mes),

22.6 (5-CH2), 21.8 (4-CH2), 21.0 (p-CH3Mes).

S6

31P{1H} NMR (202 MHz, dichloromethane-d2, 299 K): δ -56.5 (1/2 ~ 3 Hz).

Figure S1: 1H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of compound 9

Figure S2: 13C{1H} NMR (126 MHz, dichloromethane-d2, 299 K) spectrum of compound 9

S7

Figure S3: 31P{1H} 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 C46H38BF10P: C: 67.17; H: 4.66. Found: C: 66.78; H: 4.60.

1H NMR (600 MHz, dichloromethane-d2, 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, 3JHH = 16.3 Hz, 1H, =CH), 6.97 (d, 4JPH = 3.5 Hz, 1H, m-

Mesa), 6.81 (s, 1H, m’-Mesa), 6.79 (m, 1H, m-Mesb), 6.40 (d, 3JHH = 16.3 Hz, 1H, =CHPh), 6.38

(d, 4JPH = 2.5 Hz, 1H, m’-Mesb), 5.87 (s, 1H, 2-CH), 2.57 (s, 3H, o-CH3Mes,b), 2.45 (m, 3H, o-

CH3Mes,a), 2.30, 2.20 (each m, each 1H, 3-CH2)t, 2.23 (s, 3H, p-CH3

Mes,a), 2.20 (s, 3H, o’-

S8

CH3Mes,a), 2.10 (s, 3H, p-CH3

Mes,b), 1.77, 1.70 (each m, each 1H, 5-CH2)t, 1.65, 1.52 (each m,

each 1H, 4-CH2)t, 1.61 (s, 3H, o’-CH3Mes,b), 1.58, 1.43 (each m, each 1H, 6-CH2)t. [t tentatively

assigned]

13C{1H} NMR (151 MHz, dichloromethane-d2, 213 K): δ 166.3 (d, 2JPC = 29.6 Hz, BC=), 143.1

(d, 2JPC = 17.8 Hz, o-Mesa), 143.0 (o’-Mesa), 142.5 (d, 2JPC = 3.4 Hz, o-Mesb), 141.3 (d, 4JPC =

2.4 Hz, p-Mesa), 139.9 (p-Mesb) , 139.8 (d, 2JPC = 10.2 Hz, o’-Mesb), 138.7 (d, 1JPC = 50.6 Hz,

PC=), 136.3 (=CHPh), 136.1 (i-Ph), 133.2 (d, 2JPC = 3.3 Hz, 1-C=), 130.2 (d, 3JPC = 8.3 Hz, m-

Mesb), 130.0 (d, 3JPC = 8.3 Hz, 2-CH), 129.6 (d, 3JPC = 5.9 Hz, m’-Mesa), 129.3 (d, 3JPC = 9.2 Hz,

m-Mesa), 129.2 (d, 3JPC = 9.2 Hz, m’-Mesb), 128.3 (m-Ph), 128.1 (p-Ph), 126.6 (o-Ph), 125.4

(d, 1JPC = 25.3 Hz, i-Mesa), 124.6 (d, 1JPC = 39.9 Hz, i-Mesb), 124.4 (d, 3JPC = 46.8 Hz, =CH),

27.4 (5-CH2)t, 25.3 (3-CH2)t, 25.0 (br d, 3JPC = 13.5 Hz, o-CH3Mes,b), 23.7 (dm, J = 8.7 Hz, o-

CH3Mes,a), 22.4 (6-CH2)t, 22.3 (d, 3JPC = 2.2 Hz, o’-CH3

Mes,a), 22.0 (dd, J = 9.5 Hz, J = 3.9 Hz,

o’-CH3Mes,b), 21.5 (4-CH2)t, 20.7 (p-CH3

Mes,a), 20.1 (p-CH3Mes,b). [C6F5 not listed; t tentatively

assigned]

31P{1H} NMR (243 MHz, dichloromethane-d2, 213 K): δ 8.8 (partial relaxed 1:1:1:1 q, JPB ~

25 Hz).

11B{1H} NMR (192 MHz, dichloromethane-d2, 213 K): δ −2.0 (1/2 ~ 1900 Hz)

19F NMR (564 MHz, dichloromethane-d2, 213 K): δ -125.4 (m, o), -131.7 (m, o’), -158.0 (t, 3JFF

= 21.3 Hz, p), -163.8 (m, m’), -164.6 (m, m)(each 1F, C6F5)[19Fmp = 5.8, 6.6], -128.4 (o), -

130.7 (o’), -159.4 (m, p), -165.6 (m, m’), -165.9 (m, m)(each 1F, C6F5)[19Fmp = 6.2, 6.5].

Figure S4: 1H NMR (600 MHz, dichloromethane-d2, 213 K) spectrum of compound 10a

S9

Figure S5: 13C{1H} NMR (151 MHz, dichloromethane-d2, 213 K) spectrum of compound 10a

Figure S6: 11B{1H} NMR (192 MHz, dichloromethane-d2, 213 K) and 31P{1H} NMR (243 MHz, dichloromethane-d2, 213 K) spectra of compound 10a

S10

Figure S7: 19F NMR (564 MHz, dichloromethane-d2, 213 K) spectrum of compound 10a

Figure S8: Dynamic 1H NMR (600 MHz, dichloromethane-d2) spectra of compound 10a

S11

Figure S9: Dynamic 19F NMR (564 MHz, dichloromethane-d2) spectra of compound 10a

G‡[Tc, (T)] = RTc(22.96 + ln(Tc/)) [J/mol]

Tc = coalescence temperature [K]: 286 K (19F, p-BC6F5)

= chemical shift difference [Hz] (19F, p-BC6F5, 233 K): 883 Hz

R = 8.314 J/(mol·K); 1 J = 0.239 cal

G‡[286 K, (233 K) = 883 Hz] = 51913 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 C46H38BF10P, M = 822.54,

colourless crystal, 0.15 x 0.10 x 0.06 mm, a = 12.4191(2), b = 13.0158(2), c = 15.8780(3) Å, α

= 106.250(1), β = 105.633(1), γ = 92.883(1)°, V = 2350.9(1) Å3, ρcalc = 1.162 gcm-3, μ = 0.126

mm-1, empirical absorption correction (0.981 ≤ T ≤ 0.992), Z = 2, triclinic, space group P1 (No.

2), λ = 0.71073 Å, T = 223(2) K, ω and φ scans, 20532 reflections collected (±h, ±k, ±l), 7974

independent (Rint = 0.047) and 6146 observed reflections [I>2σ(I)], 529 refined parameters, R

= 0.070, wR2 = 0.191, max. (min.) residual electron density 0.31 (-0.31) e.Å-3, hydrogen atoms

were calculated and refined as riding atoms.

S12

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),

S13

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.


1H NMR (500 MHz, dichloromethane-d2, 213 K): δ 6.95 (d, 4JPH = 3.0 Hz, 1H, m-Mesa), 6.78 (s,

1H, m’-Mesa), 6.76 (s, 1H, m’-Mesb), 6.34 (s, 1H, m-Mesb), 6.15 (d, 3JHH = 16.0 Hz, 1H, =CH),

5.72 (s, 1H, 2-CH), 5.62 (d, 3JHH = 16.0 Hz, 1H, =CHtBu), 2.53 (s, 3H, o´-CH3Mes,b), 2.44 (br, 3H,

o-CH3Mes,a), 2.21 (s, 3H, p-CH3

Mes,a), 2.18, 2.13 (each m, each 1H, 3-CH2)t, 2.16 (s, 3H, o´-

CH3Mes,a), 2.09 (s, 3H, p-CH3

Mes,b), 1.71, 1.67 (each br m, each 1H, 5-CH2)t, 1.59, 1.45 (each

m, each 1H, 4-CH2), 1.56 (s, 3H, o-CH3Mes,b), 1.53, 1.40 (each m, each 1H, 6-CH2), 0.75 (s,

9H, CH3tBu). [t tentatively assigned]

13C{1H} NMR (126 MHz, dichloromethane-d2, 213 K): δ 167.9 (br d, 2JPC = 30 Hz, BC=), 151.9

(=CHtBu), 143.1 (d, 2JPC = 17.2 Hz, o-Mesa), 143.0 (o´-Mesa), 142.5 (d, 2JPC = 3.4 Hz, o´-Mesb),

141.1 (d, 4JPC = 1.7 Hz, p-Mesa), 139.7 (d, 2JPC = 13.2 Hz, o-Mesb), 139.7 (d, 4JPC = 2.1 Hz, p-

Mesb), 135.5 (d, 1JPC = 51.1 Hz, PC=), 133.0 (d, 2JPC = 3.5 Hz, 1-C=), 130.1 (d, 3JPC = 8.2 Hz,

m´-Mesb), 129.5 (d, 3JPC = 6.9 Hz, 2-CH), 129.5 (d, 3JPC = 6.9 Hz, m‘-Mesa), 129.3 (d, 3JPC =

9.1 Hz, m-Mesa), 129.1 (d, 3JPC = 9.1 Hz, m-Mesb), 125.6 (d, 1JPC = 25.0 Hz, i-Mesa), 124.8 (d,

1JPC = 39.6 Hz, i-Mesb), 120.2 (d, 3JPC = 45.5 Hz, =CH), 33.3 (CtBu), 28.0 (CH3tBu), 27.4 (5-CH2)t,

25.2 (3-CH2)t, 24.9 (m, o´-CH3Mes,b), 23.6 (m, o-CH3

Mes,a), 22.4 (6-CH2)t, 22.3 (d, 3JPC = 2.3 Hz,

o‘-CH3Mes,a), 22.0 (dd, J = 9.3 Hz, J = 3.4 Hz, o-CH3

Mes,b), 21.5 (4-CH2)t, 20.7 (p-CH3Mes,a), 20.0

(p-CH3Mes,b). [C6F5 not listed; t tentatively assigned]

31P{1H} NMR (202 MHz, dichloromethane-d2, 213 K): δ 10.9 (partial relaxed 1:1:1:1 q JPB ~

26 Hz).

31P{1H} NMR (202 MHz, dichloromethane-d2, 299 K): δ 12.8 (1/2 ~ 37 Hz).

11B{1H} NMR (160 MHz, dichloromethane-d2, 213 K): δ -3.0 (ν1/2 ~ 2400 Hz).

19F NMR (470 MHz, dichloromethane-d2, 213 K): δ -125.9 (m, o), -131.2 (m, o´), -158.7 (br t,

3JFF = 21.3 Hz, p), 164.7 (m, m), -164.9 (m, m’)(each 1F, C6F5)[19Fm,p = 6.0, 6.2]; -128.8 (m,

o), -130.7 (m, o´), -159.8 (br t, 3JFF = 17.0 Hz, p), -165.9 (m, m´), -166.1 (m, m)(each 1F,

C6F5)[19Fm,p = 6.1, 6.3]

S14

Figure S11: 1H NMR (500 MHz, dichloromethane-d2, 213 K) spectrum of compound 10b

Figure S12: 13C{1H} NMR (126 MHz, dichloromethane-d2, 213 K) spectrum of compound 10b

S15

Figure S13: 19F NMR (470 MHz, dichloromethane-d2, 213 K) spectrum of compound 10b

Figure S14: 31P{1H} NMR (202 MHz, dichloromethane-d2) spectra of compound 10b at 299 K (1) and 213 K (2)

Figure S15: 11B{1H} NMR (160 MHz, dichloromethane-d2) spectra of compound 10b at 299 K (1) and 213 K (2)

S16

Figure S16: Dynamic 1H NMR (500 MHz, dichloromethane-d2) spectra of compound 10b

Figure S17: Dynamic 19F NMR (470 MHz, dichloromethane-d2) spectra of compound 10b

S17


Tc= coalescence temperature [K]: 286 K (19F, p-BC6F5)


R = 8.314 J/(mol·K); 1 J = 0.239 cal

G‡[286 K, (233 K) = 567 Hz] = 52967 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 C44H42BF10P, M = 802.56,

colourless crystal, 0.22 x 0.06 x 0.01 mm, a = 12.7265(3), b = 13.0670(3), c = 15.1809(6) Å, α

= 103.041(1), β = 98.995(1), γ = 102.917(2)°, V = 2339.7(1) Å3, ρcalc = 1.139 gcm-3, μ = 0.125

mm-1, empirical absorption correction (0.973 ≤ T ≤ 0.998), Z = 2, triclinic, space group P1 (No.

2), λ = 0.71073 Å, T = 223(2) K, ω and φ scans, 21518 reflections collected (±h, ±k, ±l), 8122

independent (Rint = 0.067) and 5633 observed reflections [I>2σ(I)], 603 refined parameters, R

= 0.087, wR2 = 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)

S18


Scheme S4

A solution of compound 10a (515.2 mg, 626.3 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, 552.2 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.


A solution of the white solid in dichloromethane-d2 showed at 213 K a mixture of two isomers

11 and 11’ [ratio ca. 77 : 23 (31P)].

Major component (11):

1H NMR (500 MHz, dichloromethane-d2, 213 K): δ 7.29 (m, 2H, m-Ph), 7.22 (m, 2H, o-Ph),

7.19 (m, 1H, p-Ph), 7.00 (d, 4JPH = 3.2 Hz, 1H, m-Mesa), 6.79 (m, 1H, m-Mesb), 6.78 (m, 1H,

m’-Mesa), 6.51 (m, 1H, m’-Mesb), 5.88 (br, 1H, 3-CH), 4.14 (br d, J = 10.3 Hz, 1H, 4-CH), 2.62

(s, 3H, o-CH3Mes,b), 2.45 (s, 3H, o-CH3

Mes,a), 2.34 (m, 1H, 5-CH), 2.26 (s, 3H, p-CH3Mes,a), 2.15

(s, 3H, p-CH3Mes,b), 2.09 (2H), 1.47 (1H), 1.07 (1H), 1.29 (1H), 0.63 (1H), 1.17 (1H), 0.81

(1H)(each m, CH2), 1.96 (s, 3H, o’-CH3Mes,b), 1.83 (s, 3H, o’-CH3

Mes,a).

13C{1H} NMR (126 MHz, dichloromethane-d2, 213 K): δ 153.1 (br dm, J = 3.8 Hz, 10-C)t, 145.7

(br, 2-C)t, 143.8 (d, 2JPC = 19.1 Hz, o-Mesa), 142.6 (i-Ph)t, 142.6 (d, 2JPC = 6.5 Hz, o-Mesb),

142.0 (d, 2JPC = 6.5 Hz, o’-Mesa), 141.7 (d, 2JPC = 14.9 Hz, o’-Mesb), 141.0 (d, 4JPC = 3.1 Hz, p-

Mesa), 140.7 (d, 4JPC = 2.1 Hz, p-Mesb), 131.2 (d, 3JPC = 7.2 Hz, m’-Mesa), 130.3 (d, 3JPC =

11.2 Hz, m-Mesa), 130.1 (d, 3JPC = 7.8 Hz, m-Mesb), 128.6 (o-Ph), 128.3 (d, 3JPC = 9.9 Hz, m’-

Mesb), 127.8 (m-Ph), 126.0 (d, 1JPC = 53.5 Hz, 1-C), 125.8 (p-Ph), 124.7 (br d, J = 42.7 Hz 3-

CH), 123.8 (d, 1JPC = 41.9 Hz, i-Mesb), 121.7 (d, 1JPC = 25.6 Hz, i-Mesa), 47.9 (d, 3JPC = 10.9 Hz,

S19

5-CH), 45.6 (4-CH), 33.5 (dm, J = 6.8 Hz), 27.8, 27.6, 25.8 (CH2), 25.4 (d, 3JPC = 10.5 Hz, o-

CH3Mes,a), 24.3 (d, 3JPC = 3.3 Hz, o’-CH3

Mes,a), 22.9 (m, o-CH3Mes,b), 20.7 (m, o’-CH3

Mes,b), 20.6

(d, J = 1.4 Hz, p-CH3Mes,a), 20.3 (d, J = 1.1 Hz, p-CH3

Mes,b). [C6F5 not listed, t tentatively

assigned].

31P{1H} NMR (202 MHz, dichloromethane-d2, 213 K): δ 10.4 (1/2 ~ 40 Hz)

11B{1H} NMR (160 MHz, dichloromethane-d2, 213 K): δ 3.6 (broad).

11B{1H} NMR (160 MHz, dichloromethane-d2, 299 K): δ 6.4 (1/2 ~ 550 Hz)

19F NMR (470 MHz, dichloromethane-d2, 213 K): δ -124.5, -126.0, -129.3, -130.1 (each br,

each 1F, o-C6F5), -158.4 (br t, 3JFF = 19.7 Hz), -159.5 (br t, 3JFF = 20.8 Hz)(each 1F, p-C6F5), -

164.6, -165.6 (each m, each 2F, m-C6F5).

Minor component (11’):


7.14 (m, 1H, p-Ph), 7.01 (br, 1H, m-Mesa), 6.94 (br, 1H, m-Mesb), 6.80 (br, 1H, m’-Mesa), 6.47

(br, 1H, m’-Mesb), 5.92 (br, 1H, 3-CH), 3.47 (br m, 1H, 4-CH), 2.78 (m, 1H, 5-CH), 2.76 (s, 3H,

o-CH3Mes,b), 2.27 (s, 3H, p-CH3

Mes,a), 2.21 (s, 3H, o-CH3Mes,a), 2.18 (s, 3H, p-CH3

Mes,b), 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, CH2), 1.98

(s, 3H, o’-CH3Mes,b), 1.76 (s, 3H, o’-CH3

Mes,a).

13C{1H} NMR (126 MHz, dichloromethane-d2, 213 K): δ 149.8 (br d, J = .4.2 Hz, 10-C), 144.2

(d, 2JPC = 20.0 Hz, o-Mesa), 142.8 (m, o-Mesb), 142.6 (i-Ph)t, 142.2 (m, o’-Mesb), 142.0 (m, p-

Mesa), 141.9 (d, 2JPC = 6.5 Hz, o’-Mesa), 141.1 (m, p-Mesb), 131.7 (d, 3JPC = 8.2 Hz, m’-Mesa),

130.2 (d, 3JPC = 10.1 Hz, m-Mesa), 129.9 (d, 3JPC = 8.2 Hz, m-Mesb), 128.7 (o-Ph), 128.4 (d,

1JPC = 53.2 Hz, 1-C), 128.0 (m, m’-Mesb), 128.0 (m-Ph), 126.2 (br, 3-CH), 125.8 (p-Ph), 123.6

(d, 1JPC = 41.6 Hz, i-Mesb), 120.3 (d, 1JPC = 26.6 Hz, i-Mesa), 45.4 (br, 4-CH), 39.8 (d, 3JPC =

9.6 Hz, 5-CH), 31.7 (d, 3JPC = 8.2 Hz), 28.5, 25.2, 23.3 (CH2), 24.2 (d, 3JPC = 3.3 Hz, o’-

CH3Mes,a), 24.2 (d, 3JPC = 9.0 Hz, o-CH3

Mes,a), 21.4 (m, o-CH3Mes,b), 20.7 (m, o’-CH3

Mes,b), 20.6

(m, p-CH3Mes,a), 20.4 (p-CH3

Mes,b), n.o. 2-C. [C6F5 not listed, t tentatively assigned].

31P{1H} NMR (202 MHz, dichloromethane-d2, 213 K): δ 12.7 (partial relaxed br 1:1:1:1 q, 1JPB

~ 15 Hz)


11B{1H} NMR (160 MHz, dichloromethane-d2, 299 K): δ 6.4 (1/2 ~ 550 Hz)

19F NMR (470 MHz, dichloromethane-d2, 213 K): δ -121.7, -127.4, -129.9, -130.1 (each m,

each 1F, o-C6F5), -158.1 (br t, 3JFF = 19.8 Hz), -159.6 (t, 3JFF = 20.2 Hz)(each 1F, p-C6F5), -

164.5 (2F), -165.4 (1F), 165.5 (1F)(each m, m-C6F5).

S20

Figure S19: 1H NMR (500 MHz, dichloromethane-d2, 213 K) spectrum of compound 11 [admixed with pentane]

Figure S20: 13C{1H} NMR (126 MHz, dichloromethane-d2, 213 K) spectrum of compound 11 [admixed with

pentane]

S21

Figure S21: 19F NMR (470 MHz, dichloromethane-d2, 213 K) spectrum of compound 11

Figure S22: 31P{1H} NMR (202 MHz, dichloromethane-d2) spectra of compound 11 at 299 K (1) and 213 K (2).

Figure S23: 11B{1H} NMR (160 MHz, dichloromethane-d2) spectra of compound 11 at 299 K (1) and 213 K (2)

S22

Figure S24: Dynamic 1H NMR (500 MHz, dichloromethane-d2) spectra of compound 11 [admixed with pentane]

Figure S25: Dynamic 19F NMR (470 MHz, dichloromethane-d2) spectra of compound 11

S23



= chemical shift difference [Hz]: (19F, p-BC6F5, 233 K): 476 Hz

R = 8.314 J/(mol·K); 1 J = 0.239 cal

G‡[286 K, (233 K) = 476 Hz] = 53.383 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

C46H38BF10P C5H12, approximate dimensions 0.050 mm x 0.100 mm x 0.120 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 48383 reflections to a maximum θ angle

of 25.35° (0.83 Å resolution), of which 7874 were independent (average redundancy 6.145,

completeness = 99.9%, Rint = 10.95%, Rsig = 6.65%) and 5407 (68.67%) were greater than

2σ(F2). The final cell constants of a = 14.4106(7) Å, b = 21.7070(9) Å, c = 14.5170(5) Å, β =

108.8030(10)°, volume = 4298.7(3) Å3, are based upon the refinement of the XYZ-centroids of

9539 reflections above 20 σ(I) with 4.782° < 2θ < 52.77°. Data were corrected for absorption

effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent

transmission was 0.943. The calculated minimum and maximum transmission coefficients

(based on crystal size) are 0.9830 and 0.9930. 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, C46H38BF10P C5H12. The final anisotropic full-matrix least-squares refinement on

F2 with 620 variables converged at R1 = 5.00%, for the observed data and wR2 = 10.32% for

all data. The goodness-of-fit was 1.027. The largest peak in the final difference electron density

synthesis was 0.256 e-/Å3 and the largest hole was -0.255 e-/Å3 with an RMS deviation of 0.059

e-/Å3. On the basis of the final model, the calculated density was 1.382 g/cm3 and F(000),

1864 e-.

S24

Figure S26: X-ray crystal structure of compound 11 (thermal ellipsoids are shown at the 50% probability level)


Scheme S5

A solution of TEMPO (152.0 mg, 972.6 mol, 2.0 eq) in benzene (2 mL) was added to a

solution of compound 11 (400.0 mg, 486.3 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%).

S25

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.


1H NMR (500 MHz, dichloromethane-d2, 299 K): δ 7.42 (3H), 7.34 (3H)(each m, Ph, 3-CH),

6.81 (d, 4JPH = 3.2 Hz, 4H, m-Mes), 2.55 (2H), 2.37 (2H), 1.60 (4H) (each br m, CH2), 2.25 (s,

6H, p-CH3Mes), 2.09 (s, 12H, o-CH3

Mes).

13C{1H} NMR (126 MHz, dichloromethane-d2, 299 K): δ 156.6 (br d, 2JPC = 30.2 Hz, 2-C), 148.2,

(d, J = 2.8 Hz) 138.9 (d, J = 0.9 Hz), 135.9 (d, J = 8.5 Hz)(4,5,10-C)t, 148.0 (dm, 1JFC~ 240 Hz,

C6F5), 142.7 (br d, 2JPC = 8.9 Hz, o-Mes), 142.5 (d, J = 1.9 Hz, i-Ph), 141.2 (br d, 4JPC = 2.9 Hz

p-Mes), 140.2 (dm, 1JFC~ 250 Hz, C6F5), 137.0 (dm, 1JFC~ 250 Hz, C6F5), 134.8 (d, 1JPC =

53.5 Hz, 1-C)t, 131.5 (dm, J = 46.2 Hz, 3-CH), 130.9 (br d, 3JPC = 8.9 Hz, m-Mes), 129.5, 128.4,

127.3 (p) (Ph), 127.4 (br, i-C6F5), 124.5 (br dm, 1JPC = 35.1 Hz, i-Mes), 28.7 (d, J = 1.0 Hz),

27.9 (d, J = 4.1 Hz), 23.5, 22.4 (CH2), 22.8 (br dm, 3JPC = 5.4 Hz, o-CH3Mes), 20.8 (d, J = 1.4 Hz,

p-CH3Mes). [t tentatively assigned].


11B{1H} NMR (160 MHz, dichloromethane-d2, 299 K): δ 5.7 (1/2 ~ 500 Hz).

19F NMR (470 MHz, dichloromethane-d2, 299 K): δ -128.1 (br, 2F, o-C6F5), -159.1 (t, 1F, 3JFF =

20.2 Hz, p-C6F5), -165.5 (m, 2F, m-C6F5)[19Fmp = 6.4].

1H NMR (500 MHz, dichloromethane-d2, 193 K): δ 7.39 (2H), 7.31 (4H)(each m, Ph, 3-CH),

6.94 (d, 4JPH = 2.3 Hz, 1H, m-Mesa), 6.85 (s, 1H, m’-Mesa), 6.66 (s, 1H, m-Mesb), 6.52 (d,

4JPH = 2.0 Hz, 1H, m’-Mesb), 2.55 (2H), 2.43 (1H), 1.97 (1H), 1.61 (1H), 1.52 (2H), 1.38 (1H)

(each br m, CH2), 2.25 (s, 3H, p-CH3Mes,a), 2.09 (s, 3H, p-CH3

Mes,b), 2.06 (s, 3H, o’-CH3Mes,b),

2.03 (s, 3H, o-CH3Mes,b), 1.96 (s, 3H, o-CH3

Mes,a), 1.83 (s, 3H, o’-CH3Mes,a).

13C{1H} NMR (126 MHz, dichloromethane-d2, 193 K): δ 155.0 (br d, 2JPC = 30.6 Hz, 2-C), 146.8,

137.7, 134.4 (d, J = 8.4 Hz)(4,5,10-C)t, 143.3 (d, 2JPC = 18.3 Hz, o-Mesa), 142.1 (o’-Mesa),

141.2 (m, i-Ph), 141.2 (p-Mesa), 141.1 (d, 2JPC = 16.0 Hz, o’-Mesb), 140.5 (o-Mesb), 140.2 (m,

p-Mesb), 133.7 (d, 1JPC = 54.2 Hz, 1-C)t, 131.4 (br d, 3JPC = 7.0 Hz, m’-Mesa), 130.6 (dd, J =

45.0 Hz, J = 12.0 Hz, 3-CH), 130.0 (br d, 3JPC = 10.7 Hz, m-Mesa), 129.7 (d, 3JPC = 7.4 Hz, m-

Mesb), 128.8, 128.4, 127.8, 127.5, 126.6 (p) (each br, Ph), 128.1 (d, 3JPC = 9.4 Hz, m’-Mesb),

125.5 (d, 1JPC = 40.3 Hz, i-Mesb), 120.0 (d, 1JPC = 28.5 Hz, i-Mesa), 28.2, 27.2 (d, J = 3.7 Hz),

22.6, 21.5 (CH2), 24.7 (d, 3JPC = 3.6 Hz, o’-CH3Mes,a), 22.9 (dd, J = 10.1 Hz, J = 4.0 Hz, o-

S26

CH3Mes,a), 21.0 (m, o-CH3

Mes,b), 20.7 (m, o’-CH3Mes,b), 20.5 (p-CH3

Mes,a), 20.0 (p-CH3Mes,b). [C6F5

not listed; t tentatively assigned].



19F NMR (470 MHz, dichloromethane-d2, 193 K): δ -126.2 (m, o), -130.7 (m, o’), -158.7 (br t,

3JFF = 21.4 Hz, p), -164.3 (m, m), -164.5 (m, m’)(each 1F, C6F5)[19Fmp = 5.6, 5.8], -127.6 (m,

1F, o), -129.1 (m, 1F, o’), -157.8 (br t, 1F, 3JFF = 21.6 Hz, p), -165.5 (m, 2F, m,m’)(C6F5)[19Fmp

= 7.7].

Figure S27: 1H NMR (500 MHz, dichloromethane-d2, 193 K) spectrum of compound 12 [admixed with pentane]

S27

Figure S28: 13C{1H} NMR (126 MHz, dichloromethane-d2, 193 K) spectrum of compound 12 [admixed with

pentane]


S28


Figure S31: 11B{1H} NMR (160 MHz, dichloromethane-d2) spectra of compound 12 at 299 K (1) and 193 K (2)

S29

Figure S32: Dynamic 1H NMR (500 MHz, dichloromethane-d2) spectra of compound 12 [admixed with pentane]

Figure S33: Dynamic 19F NMR (470 MHz, dichloromethane-d2) spectra of compound 12

S30




R = 8.314 J/(mol·K); 1 J = 0.239 cal

G‡[243 K, (193 K) = 426 Hz] = 45.251 J/mol = 10.8 ± 0.3 kcal/mol



X-ray crystal structure analysis of compound 12: formula C46H36BF10P, M = 820.53,

colourless crystal, 0.08 x 0.06 x 0.02 mm, a = 13.8302(3), b = 23.4539(5), c = 14.8556(3) Å, β

= 108.613(1)°, V = 4566.7(2) Å3, ρcalc = 1.193 gcm-3, μ = 0.130 mm-1, empirical absorption

correction (0.989 ≤ T ≤ 0.997), Z = 4, monoclinic, space group P21/n (No. 14), λ = 0.71073 Å,

T = 223(2) K, ω and φ scans, 27050 reflections collected (±h, ±k, ±l), 7819 independent (Rint =

0.103) and 5035 observed reflections [I>2σ(I)], 529 refined parameters, R = 0.106, wR2 =

0.234, max. (min.) residual electron density 0.90 (-0.47) e.Å-3, hydrogen atoms were calculated

and refined as riding atoms.


S31


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.


1H NMR (500 MHz, dichloromethane-d2, 253 K): δ 9.70 (d, 1JPH = 495.9 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, 3JPH = 4.1 Hz, 1H, m-Mesa), 6.84 (br d, 3JPH = 4.4 Hz, 1H, m-

Mesb), 6.82 (br d, 3JPH = 3.8 Hz, 1H, m’-Mesa), 6.77 (br d, 3JPH = 4.6 Hz, 1H, m’-Mesb), 5.90

(br, 1H, 3-CH), 3.82 (dm, 3JHH = 8.8 Hz, 1H, 4-CH), 2.66 (s, 3H, o-CH3Mes,b), 2.65 (s, 3H, o-

CH3Mes,a), 2.52/2.04, 1.72/1.24, 1.63/1.17, 1.47/0.95 (each m, each 1H, CH2), 2.34 (m, 1H, 5-

CH), 2.26 (s, 3H, p-CH3Mes,b), 2.23 (s, 3H, p-CH3

Mes,a), 1.89 (s, 3H, o’-CH3Mes,b), 1.77 (s, 3H,

o’-CH3Mes,a).

13C{1H} NMR (126 MHz, dichloromethane-d2, 253 K): δ 168.4 (d, 2JPC = 7.7 Hz, 10-C)t, 144.9

(d, 2JPC = 9.2 Hz, o-Mesb), 144.8 (d, 4JPC =2.8 Hz, p-Mesa), 144.2 (d, 4JPC = 2.8 Hz, p-Mesb),

143.4 (d, 2JPC = 11.0 Hz, o-Mesa), 142.8 (d, 2JPC = 9.4 Hz, o’-Mesa), 142.4 (i-Ph), 142.2 (d,

2JPC = 10.9 Hz, o’-Mesb), 134.6 (br dm, J = 14.2 Hz, 3-CH), 132.3 (d, 3JPC = 11.3 Hz, m’-

Mesa), 131.6 (d, 3JPC = 11.5 Hz, m-Mesb), 131.2 (o-Ph≡), 130.6 (d, 3JPC = 10.8 Hz, m’-Mesb),

130.4 (d, 3JPC = 10.7 Hz, m-Mesa), 129.0 (o-Ph), 128.2 (m-Ph), 128.1 (m-Ph≡), 126.9 (i-Ph≡),

126.5 (p-Ph≡), 126.2 (p-Ph), 118.9 (d, 1JPC = 77.8 Hz, i-Mesa), 115.5 (d, 1JPC = 83.4 Hz, i-

S32

Mesb), 113.1 (d, 1JPC = 73.1 Hz, 1-C)t, 110.3 (br 1:1:1:1 q, 1JCB ~ 80 Hz, BC≡), 98.7 (br,

PhC≡), 51.3 (d, 3JPC = 12.4 Hz, 5-CH), 43.0 (4-CH), 35.0 (d, 3JPC = 9.8 Hz), 31.7, 29.2, 26.3

(CH2), 23.8 (d, 3JPC = 10.7 Hz, o-CH3Mes,a), 22.3 (d, 3JPC = 5.8 Hz, o’-CH3

Mes,a), 21.5 (d, 3JPC =

4.4 Hz, o-CH3Mes,b), 21.1 (p-CH3

Mes,a), 20.9 (p-CH3Mes,b), 20.4 (d, 3JPC = 10.4 Hz, o’-CH3

Mes,b),

n.o. (2-C). [C6F5 not listed; t tentatively assigned].

31P NMR (202 MHz, dichloromethane-d2, 253 K): δ -29.3 (d, 1JPH = 496.6 Hz).

31P{1H} NMR (202 MHz, dichloromethane-d2, 253 K): δ -29.3 (1/2 ~ 15 Hz ).


19F NMR (470 MHz, dichloromethane-d2, 253 K): δ -129.2 (br, 2F, o), -162.5 (t, 3JFF = 20.8 Hz,

1F, p), -166.5 (m, 2F, m)(C6F5)[19Fmp = 3.2], -129.6 (m, 2F, o), -161.0 (t, 3JFF = 20.7 Hz, 1F,

p), -165.9 (m, 2F, m)(C6F5)[19Fmp = 4.9].


S33

Figure S36: 13C NMR (126 MHz, dichloromethane-d2, 253 K) spectrum of compound 13


S34

Figure S38: 31P{1H} NMR (1) and 31P NMR (2) (202 MHz, dichloromethane-d2, 253 K) spectra of compound 13

Figure S39: 11B{1H} NMR (160 MHz, dichloromethane-d2, 253 K) spectrum of compound 13


solution of compound 13 at -35 °C:


C61H52BF10P, approximate dimensions 0.180 mm x 0.180 mm x 0.200 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 40631 reflections to a maximum θ angle of 26.40°

S35

(0.80 Å resolution), of which 10234 were independent (average redundancy 3.970,








Bruker SHELXTL Software Package, using the space group P 1 n 1, with Z = 2 for the formula

unit, C61H52BF10P. The final anisotropic full-matrix least-squares refinement on F2 with 669

variables converged at R1 = 3.89%, for the observed data and wR2 = 8.45% for all data. The

goodness-of-fit was 1.042. The largest peak in the final difference electron density synthesis

was 0.194 e-/Å3 and the largest hole was -0.226 e-/Å3 with an RMS deviation of 0.045 e-/Å3.

On the basis of the final model, the calculated density was 1.349 g/cm3 and F(000), 1056 e-.


S36


Scheme S7

A yellow solution of compound 12 (200.0 mg, 243.7 mol, 1.0 eq) in CH2Cl2 (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, 213.6 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.


1H NMR (600 MHz, dichloromethane-d2, 299 K): δ 9.48 (d, 1JPH = 507.3 Hz, 1H, PH), 7.38 (m,

2H, m-Ph), 7.31 (m, 1H, p-Ph), 7.24 (m, 2H, o-Ph), 7.22 (d, 4JPH = 5.5 Hz, 1H, 3-CH), 7.07 (d,

4JPH = 4.4 Hz, 1H, m-Mesa), 7.00 (d, 4JPH = 4.6 Hz, 1H, m-Mesb), 6.96 (d, 1H, 4JPH = 3.5 Hz,

m’-Mesa), 6.81 (d, 4JPH = 4.4 Hz, 1H, m’-Mesb), 3.90 (partial relaxed 1:1:1:1 q, 1JBH ~ 85 Hz,

1H, BH), 2.67/ 2.20 (each m, each 1H, 9-CH2)t, 2.54 (m, 2H, 6-CH2)t, 2.34 (s, 3H, p-CH3Mes,a),

2.32 (s, 3H, p-CH3Mes,b), 2.31 (s, 3H, o-CH3

Mes,a), 2.23 (s, 3H, o-CH3Mes,b), 2.14 (s, 3H, o’-

CH3Mes,b), 1.91 (s, 3H, o’-CH3

Mes,a), 1.69 (1H), 1.50 (2H), 1.39 (1H)(each m, 7,8-CH2)t. [t

tentatively assigned]

13C{1H} NMR (151 MHz, dichloromethane-d2, 299 K): δ 146.5 (d, 4JPC = 3.9 Hz, 4-C), 145.2 (d,

4JPC = 2.8 Hz, p-Mesb), 144.9 (d, 4JPC = 3.0 Hz, p-Mesa), 144.4 (d, 2JPC = 10.1 Hz, o’-Mesb),

143.6 (d, 2JPC = 11.8 Hz, o-Mesa), 143.4 (d, 2JPC = 8.4 Hz, o’-Mesa), 142.7 (d, 2JPC = 9.9 Hz, o-

Mesb), 142.0 (d, J = 0.9 Hz, i-Ph), 141.6 (d, 2JPC = 14.2 Hz, 10-C)t, 137.4 (br d, 3JPC = 16.8 Hz,

3-CH), 134.6 (d, 3JPC = 12.4 Hz, 5-C)t, 132.6 (d, 3JPC = 11.0 Hz, m’-Mesa), 132.1 (d, 3JPC =

11.5 Hz, m’-Mesb), 131.6 (d, 3JPC = 10.6 Hz, m-Mesa), 130.8 (d, 3JPC = 10.5 Hz, m-Mesb), 129.4

(o-Ph), 128.4 (m-Ph), 127.3 (p-Ph), 120.5 (d, 1JPC = 83.1 Hz, 1-C), 117.1 (d, 1JPC = 76.3 Hz, i-

Mesa), 116.2 (d, 1JPC = 80.9 Hz, i-Mesb), 32.1 (d, 3JPC = 7.7 Hz, 9-CH2)t, 28.1 (d, 4JPC = 1.6 Hz,

S37

6-CH2)t, 22.5 (7,8-CH2)t, 22.4 (d, 3JPC = 5.2 Hz, o’-CH3Mes,a), 21.4 (d, J = 1.4 Hz, p-CH3

Mes,a),

21.3 (d, 3JPC = 11.5 Hz, o-CH3Mes,a), 21.2 (p-CH3

Mes,b), 21.1 (br d, 3JPC = 6.1 Hz, o’-CH3Mes,b),

21.0 (d, 3JPC = 11.9 Hz, o-CH3Mes,b), n.o. (2-C).[C6F5 not listed; t tentatively assigned]

31P NMR (243 MHz, dichloromethane-d2, 299 K): δ -28.5 (br d, 1JPH ~ 508 Hz).

31P{1H} NMR (243 MHz, dichloromethane-d2, 299 K): δ -28.5 (m).

11B NMR (192 MHz, dichloromethane-d2, 299 K): δ −20.8 (d, 1JBH ~ 83 Hz)


19F NMR (564 MHz, dichloromethane-d2, 299 K): δ -130.9 (m, 2F, o), -163.2 (t, 3JFF = 20.1 Hz,


p), -166.3 (m, 2F, m)(C6F5)[19Fmp = 3.6].


S38



Figure S44: 31P{1H} NMR (1) and 31P NMR (2) (243 MHz, dichloromethane-d2, 299 K) spectra of compound 14

S39

Figure S45: 11B{1H} NMR (1) and 11B 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 C46H38BF10P CH2Cl2, M =

907.47, colourless crystal, 0.07 x 0.06 x 0.04 mm, a = 11.7476(3), b = 13.4169(3), c =

15.7177(5) Å, α = 106.742(1), β = 103.703(1), γ = 107.436(2)°, V = 2117.0(1) Å3, ρcalc = 1.424

gcm-3, μ = 0.270 mm-1, empirical absorption correction (0.981 ≤ T ≤ 0.989), Z = 2, triclinic,

space group P1 (No. 2), λ = 0.71073 Å, T = 223(2) K, ω and φ scans, 10482 reflections

collected (±h, ±k, ±l), 7274 independent (Rint = 0.038) and 4952 observed reflections [I>2σ(I)],

592 refined parameters, R = 0.085, wR2 = 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.

S40


Generation of compound 14-D2

Scheme S8

A yellow solution of compound 12 (20.0 mg, 24.4 mol, 1.0 eq) in CD2Cl2 (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-D2 (12 : 14-D2 ~ 54 : 46 (31P{1H}) was observed.

S41

The NMR data of compounds 14-D2 and 12 are consistent with those listed for isolated

compounds 14 and 12 (see above).

Compound 14-D2

2H NMR (92 MHz, dichloromethane, 299 K): δ 9.46 (d, 1JPD = 77.1 Hz, 1D, PD), 3.88 (br, 1D,

BD).

31P NMR (243 MHz, dichloromethane-d2, 299 K): δ -28.6 (br 1:1:1 t, 1JPD ~ 79 Hz).

31P{1H} NMR (243 MHz, dichloromethane-d2, 299 K): δ -28.6 (br 1:1:1 t, 1JPD ~ 79 Hz).

11B NMR (192 MHz, dichloromethane-d2, 299 K): δ −21.0 (1/2 ~ 70 Hz)


19F NMR (564 MHz, dichloromethane-d2, 299 K): δ -131.0, -133.0 (each m, each 2F, o), -162.7,

-163.3 (each t, 3JFF = 20.1 Hz, each 1F, p), -166.3, -166.9 (each m, each 2F, m)(C6F5).

Figure S47: 1H NMR (600 MHz, dichloromethane-d2, 299 K) spectra of (1) the isolated compound 14 and (2) the reaction of compound 12 with D2; (3) 1H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of the isolated

compound 12.

S42

Figure S48: 19F NMR (564 MHz, dichloromethane-d2, 299 K) spectra of (1) the isolated compound 14 and (2) the reaction of compound 12 with D2; (3) 19F NMR (470 MHz, dichloromethane-d2, 299 K) spectrum the isolated

compound 12.

Figure S49: 2H NMR (92 MHz, dichloromethane, 299 K) spectrum of the reaction compound 12 with D2

S43

Figure S50: (1) 11B{1H} and (2) 11B NMR (192 MHz, dichloromethane-d2, 299 K) spectra of the isolated compound 14; (3) 11B NMR (192 MHz, dichloromethane-d2, 299 K) spectrum of the reaction of compound 12 with

D2; (4) 11B NMR (160 MHz, dichloromethane-d2, 299 K) spectrum of the isolated compound 12

Figure S51: (1) 31P{1H} and (2) 31P NMR (243 MHz, dichloromethane-d2, 299 K) spectra of the isolated compound 14; (3) 31P NMR (243 MHz, dichloromethane-d2, 299 K) spectrum of the reaction of compound 12 with

D2; (5) 31P NMR (202 MHz, dichloromethane-d2, 299 K) spectrum of the isolated compound 12

S44


Scheme S9

A solution of dimethylacetylenedicarboxylate (17.9 L, 20.7 mg, 145.9 mol, 1.0 eq) in

toluene (1 mL) was added to a solution of compound 11 (120.0 mg, 145.9 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 C52H44BF10O4P: C: 64.74; H: 4.60. Found: C: 64.99; H: 4.73.

A solution of the yellow solid in dichloromethane-d2 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 (31P)].

[Ar = 4,6-dimethylphenylene]

Major component 17:

1H NMR (600 MHz, dichloromethane-d2, 299 K): δ 7.23 (m, 2H, m-Ph), 7.17 (m, 1H, p-Ph),

7.11 (m, 1H, 3-CHAr), 7.00 (m, 2H, o-Ph), 6.97 (br d, 4JPH = 5.5 Hz, 1H, 5-CHAr), 6.75 (br d,

4JPH = 2.7 Hz, 1H, m-Mes), 6.57 (br d, 4JPH = 3.9 Hz, 1H, m’-Mes), 5.86 (m, 1H, 3-CH), 3.95

(dm, 3JHH = 10.8 Hz, 1H, 4-CH), 3.68 (s, 3H, OMeC=O), 3.49 (s, 3H, OMe), 2.72 (s, 3H, o’-

CH3Mes), 2.55/2.06 (each m, each 1H, 9-CH2), 2.35 (s, 3H, 4-CH3

Ar), 2.35 (m, 1H, 5-CH), 2.25

S45

(s, 3H, o-CH3Mes), 2.20 (s, 3H, p-CH3

Mes), 2.07 (s, 3H, 6-CH3Ar), 1.91 (s, 3H, CH3), 1.53, 1.16

(each m, each 1H, 7-CH2), 1.33/1.02 (each m, each 1H, 6-CH2), 1.30/0.94 (each m, each 1H,

8-CH2).

13C{1H} NMR (151 MHz, dichloromethane-d2, 299 K): δ 174.7 (d, 3JPC = 6.9 Hz, O=C), 165.8

(d, 2JPC = 18.3 Hz, O2C=), 154.6 (d, 2JPC = 21.8 Hz, 2-CAr), 148.4 (d, 2JPC = 6.7 Hz, 10-C), 145.9

(d, 2JPC = 10.0 Hz, o-Mes), 145.7 (d, 4JPC = 2.7 Hz, 4-CAr), 145.2 (d, 2JPC = 12.7 Hz, o’-Mes),

144.1 (d, 4JPC = 2.9 Hz, p-Mes), 142.8 (i-Ph), 141.8 (d, 2JPC = 10.3 Hz, 6-CAr), 140.3 (br, 2-C),

138.6 (br, 3-CH), 133.0 (d, 3JPC = 10.3 Hz, 5-CHAr), 132.1 (d, 3JPC = 12.3 Hz, m’-Mes), 131.9

(d, 3JPC = 11.0 Hz, m-Mes), 129.1 (o-Ph), 128.5 (m-Ph), 126.5 (p-Ph), 124.6 (d, 1JPC = 81.6 Hz,

1-C), 123.9 (d, 1JPC = 86.5 Hz, 1-CAr), 123.6 (d, 3JPC = 10.2 Hz, 3-CHAr), 117.0 (d, 1JPC =

82.0 Hz, i-Mes), 71.8 (d, 1JPC = 116.9 Hz, PC=), 56.7 (d, 2JPC = 15.3 Hz, CMe), 53.7 (OMe),

52.4 (OMeC=O), 48.4 (d, 3JPC = 13.0 Hz, 5-CH), 43.8 (d, 4JPC = 2.1 Hz, 4-CH), 33.5 (d, 3JPC =

9.4 Hz, 9-CH2), 29.7 (CH3), 29.5 (m, 6-CH2), 28.6 (d, J = 1.5 Hz, 8-CH2), 26.6 (7-CH2), 24.9

(m, o’-CH3Mes), 23.8 (d, 3JPC = 6.8 Hz, o-CH3

Mes), 21.7 (d, J = 1.3 Hz, 4-CH3Ar), 20.9 (d, 3JPC =

3.7 Hz, 6-CH3Ar), 20.7 (p-CH3

Mes). [C6F5 not listed]




= 20.2 Hz, p), -165.4 (m, m’), -166.1 (m, m)(each 1F, C6F5)[19Fmp = 4.5, 5.1], -130.4 (m, o),

-133.2 (m, o’), -162.6 (t, 3JFF = 20.4 Hz, p), -166.3 (m, m’), -168.2 (m, m)(each 1F, C6F5)[19Fmp

= 3.7, 5.5].

Minor component:



19F NMR (564 MHz, dichloromethane-d2, 299 K): δ -127.0, -129.7, -132.3, -136.9 (each br,

each 1F, o), -160.5, -162.9 (each br, each 1F, p), not resolved (4F, m)(C6F5).

S46



S47





solution of compound 17 at room temperature:


C52H44BF10O4P, approximate dimensions 0.110 mm x 0.137 mm x 0.206 mm, was used for the


S48


Bruker SAINT software package using a narrow-frame algorithm. The integration of the data











formula unit, C52H44BF10O4P. The final anisotropic full-matrix least-squares refinement on F2

with 621 variables converged at R1 = 4.87%, for the observed data and wR2 = 11.16% for all

data. The goodness-of-fit was 1.066. The largest peak in the final difference electron density



1992 e-.


S49


Scheme S10

A solution of dimethyl acetylenedicarboxylate (18.0 L, 20.8 mg, 146.2 mol, 1.0 eq) in

toluene (1 mL) was added to a solution of compound 12 (120.0 mg, 146.2 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 C52H42BF10O4P: C: 64.88; H: 4.40. Found: C: 64.91; H: 4.59.

[Ar = 4,6-dimethylphenylene]

1H NMR (500 MHz, dichloromethane-d2, 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-CHAr), 7.03

(m, 1H, 5-CHAr), 6.84 (dm, 4JPH = 3.6 Hz, 1H, m-Mes), 6.42 (dm, 4JPH = 4.6 Hz, 1H, m’-Mes),

3.66 (s, 3H. OMeC=O), 3.38 (s, 3H, OMe), 2.74/2.28 (each m, each 1H, 9-CH2)t, 2.55/2.50

(each m, each 1H, 6-CH2)t, 2.39 (d, J = 0.8 Hz, 3H, 4-CH3Ar), 2.34 (s, 3H, o-CH3

Mes)t, 2.20 (s,

3H, p-CH3Mes), 2.09 (s, 3H, 6-CH3

Ar), 1.90 (s, 3H, o’-CH3Mes)t, 1.59/1.43 (each m, each 1H, 7-

CH2)t, 1.58 (s, 3H, CH3), 1.51 (m, 2H, 8-CH2)t. [t tentatively assigned]

13C{1H} NMR (126 MHz, dichloromethane-d2, 299 K): δ 174.6 (d, 3JPC = 8.6 Hz, O=C), 162.6

(d, 2JPC = 16.3 Hz, O2C=), 154.9 (d, 2JPC = 22.4 Hz, 2-CAr), 146.0 (d, 2JPC = 9.8 Hz, o-Mes)t,

145.7 (d, 4JPC = 2.6 Hz, 4-CAr), 145.4 (d, 2JPC = 12.9 Hz, o’-Mes)t, 144.3 (d, 4JPC = 3.0 Hz, p-

S50

Mes), 143.9 (dd, J = 3.4 Hz, J = 1.1 Hz, 4-C)t, 142.1 (d, J = 1.2 Hz, i-Ph), 142.0 (d, 2JPC =

9.9 Hz, 6-CAr), 139.8 (dd, J = 18.5 Hz, J = 9.8 Hz, 3-CH), 135.8 (d, 1JPC = 80.8 Hz, 1-C),

134.8 (d, 2JPC = 11.3 Hz, 10-C)t, 134.6 (d, 3JPC = 11.5 Hz, 5-C)t, 133.2 (d, 3JPC = 10.2 Hz, 5-

CHAr), 131.7 (d, 3JPC = 6.2 Hz, m’-Mes), 131.6 (d, 3JPC = 5.1 Hz, m-Mes), 129.4 (o-Ph), 128.4

(m-Ph), 127.2 (p-Ph), 124.6 (d, 1JPC = 84.2 Hz, 1-CAr), 123.5 (d, 3JPC = 10.0 Hz, 3-CHAr),

116.3 (d, 1JPC = 82.8 Hz, i-Mes), 77.8 (d, 1JPC = 115.4 Hz, PC=), 55.7 (d, 2JPC = 15.2 Hz,

CMe), 53.7 (d, 4JPC = 1.2 Hz, OMe), 52.4 (OMeC=O), 29.4 (d, 3JPC = 7.1 Hz, 9-CH2)t, 28.7 (d,

4JPC = 1.6 Hz, 6-CH2)t, 28.2 (CH3), 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-CH2)t, 22.3 (7-CH2)t, 21.7 (d, J = 1.3 Hz, 4-CH3Ar), 20.9

(d, 3JPC = 3.4 Hz, 6-CH3Ar), 20.7 (p-Mes), n.o. (2-C). [C6F5 not listed; t tentatively assigned]




= 20.3 Hz, p), -164.9 (m, m’), -165.5 (m, m)(each 1F, C6F5)[19Fmp = 4.9, 5.5], -128.8 (m, o),

-132.6 (m, o’), -162.8 (t, 3JFF = 20.4 Hz, p), -166.2 (m, m’), -168.6 (m, m)(each 1F, C6F5)[19Fmp

= 3.4, 5.8].


S51




S52



solution of compound 18 at -35 °C:

X-ray crystal structure analysis of compound 18: A colorless plate-like specimen of

C52H42BF10O4P, approximate dimensions 0.020 mm x 0.080 mm x 0.220 mm, was used for the



Bruker SAINT software package using a wide-frame algorithm. The integration of the data




2σ(F2). The final cell constants of a = 15.1886(15) Å, b = 16.7463(17) Å, c = 18.9288(18) Å, β

= 103.662(5)°, volume = 4678.4(8) Å3, are based upon the refinement of the XYZ-centroids of




(based on crystal size) are 0.7680 and 0.9750. The final anisotropic full-matrix least-squares

refinement on F2 with 621 variables converged at R1 = 4.81%, for the observed data and wR2

= 12.26% for all data. The goodness-of-fit was 1.070. The largest peak in the final difference

electron density synthesis was 0.284 e-/Å3 and the largest hole was -0.435 e-/Å3 with an RMS

deviation of 0.057 e-/Å3. On the basis of the final model, the calculated density was 1.367 g/cm3

and F(000), 1984 e-.

S53



Scheme S11

A solution of compound 11 (200.0 mg, 243.1 mol, 1.0 eq) in CH2Cl2 (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, 195.2 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),

S54

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 C46H38BF10PNO: C: 64.80; H: 4.49; N: 1.64. Found: C: 64.63; H: 4.49; N: 1.69.



X-ray crystal structure analysis of compound 19: formula C46H38BF10NOP 2 x CH2Cl2, M

= 1022.41, colourless crystal, 0.18 x 0.05 x 0.05 mm, a = 12.6441(2), b = 14.5097(2), c =

15.1347(3) Å, α = 112.290(1), β = 96.698(1), γ = 108.846(2)°, V = 2339.0(1) Å3, ρcalc = 1.452

gcm-3, μ = 0.365 mm-1, empirical absorption correction (0.937 ≤ T ≤ 0.982), Z = 2, triclinic,

space group P1 (No. 2), λ = 0.71073 Å, T = 223(2) K, ω and φ scans, 20997 reflections

collected (±h, ±k, ±l), 8004 independent (Rint = 0.045) and 6444 observed reflections [I>2σ(I)],

657 refined parameters, R = 0.070, wR2 = 0.161, max. (min.) residual electron density 0.53 (-

0.60) e.Å-3, hydrogen atoms were calculated and refined as riding atoms.


S55


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, 164.2 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 CH2Cl2 (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, 103.6 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.



7.23 (m, 1H, p-Ph), 7.00 (d, 4JPH = 4.3 Hz, 2H, m-Mesa), 6.92 (d, 4JPH = 4.6 Hz, 2H, m-Mesb),

6.33 (br, 1H, 3-CH), 4.63 (t, J = 9.1 Hz, 1H, OH), 3.89 (br dd, 3JHH = 9.5 Hz, J = 2.0 Hz, 1H,

4-CH), 2.60/2.13 (each m, each 1H, 9-CH2), 2.37 (s, 6H, o-CH3Mes,a), 2.36 (s, 3H, p-CH3

Mes,a),

2.33 (m, 1H, 5-CH), 2.29 (s, 3H, p-CH3Mes,b), 2.20 (s, 6H, o-CH3

Mes,b), 1.56/1.13 (each m,

each 1H, 6-CH2), 1.53/1.14 (each m, each 1H, 7-CH2), 1.27/0.46 (each m, each 1H, 8-CH2).

13C{1H} NMR (126 MHz, dichloromethane-d2, 299 K): δ 159.5 (d, 2JPC = 12.8 Hz, 10-C), 144.0

(d, 4JPC = 3.0 Hz, p-Mesb), 143.8 (d, 2JPC = 11.4 Hz, o-Mesb), 143.0 (d, 4JPC = 2.9 Hz, p-Mesa),

142.9 (i-Ph), 142.0 (br, 2-C), 141.6 (d, 2JPC = 10.4 Hz, o-Mesa), 132.7 (d, 3JPC = 11.7 Hz, m-

Mesb), 132.3 (d, 3JPC = 11.7 Hz, m-Mesa), 129.3 (o-Ph), 129.2 (br m, 3-CH), 128.6 (m-Ph),

126.6 (p-Ph), 124.9 (d, 1JPC = 86.3 Hz, i-Mesa), 122.5 (d, 1JPC = 90.0 Hz, i-Mesb), 120.4 (d, 1JPC

= 99.3 Hz, 1-C), 50.5 (d, 3JPC = 13.3 Hz, 5-CH), 44.1 (4-CH), 35.6 (d, 3JPC = 7.3 Hz, 9-CH2),

30.2 (br d, 4JPC = 1.9 Hz, 8-CH2), 30.0 (br, 6-CH2), 26.9 (7-CH2), 24.2 (d, 3JPC = 4.2 Hz, o-

S56

CH3Mes,a), 23.8 (d, 3JPC = 5.4 Hz, o-CH3

Mes,b), 21.2 (d, J = 1.9 Hz, p-CH3Mes,b), 21.2 (d, J = 1.3 Hz,

p-CH3Mes,a). [C6F5 not listed]



19F NMR (470 MHz, dichloromethane-d2, 299 K): δ -128.7 (m, 2F, o), -161.5 (t, 3JFF = 20.3 Hz,


p), -165.3 (m, 2F, m)(C6F5)[19Fmp = 2.7].


S57



Figure S68 31P{1H} NMR (202 MHz, dichloromethane-d2, 299 K) spectrum of compound 20

S58


Crystals suitable for the X-ray crystal structure analysis were obtained by slow evaporation

from a dichloromethane solution of compound 20:


C46H39BF10NOP, approximate dimensions 0.080 mm x 0.180 mm x 0.200 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 22.24 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 57199 reflections to a maximum θ angle of

66.59° (0.84 Å resolution), of which 7063 were independent (average redundancy 8.098,









formula unit, C46H39BF10NOP. The final anisotropic full-matrix least-squares refinement on F2

with 551 variables converged at R1 = 4.75%, for the observed data and wR2 = 12.71% for all

data. The goodness-of-fit was 1.072. The largest peak in the final difference electron density



1760 e-.

S59



Scheme S13

A solution of compound 12 (100.0 mg, 121.9 mol, 1.0 eq) in CH2Cl2 (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

S60

(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.




X-ray crystal structure analysis of compound 21: formula C46H36BF10NOP, M = 850.54,

pale green crystal, 0.15 x 0.12 x 0.10 mm, a = 13.9970(3), b = 14.5832(3), c = 19.9467(4) Å,

β = 105.140(1)°, V = 3930.2(1) Å3, ρcalc = 1.437 gcm-3, μ = 0.156 mm-1, empirical absorption







S61


Scheme S14

1,8-Cyclohexadiene (75.4 mg, 940.6 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.


1H NMR (500 MHz, dichloromethane-d2, 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, 4JPH = 4.4 Hz, 4H, m-Mes), 4.76 (quint, J =

5.0 Hz, 1H, OH), 2.68 (m, 2H, 9-CH2), 2.56 (m, 2H, 6-CH2), 2.33 (s, 6H, p-CH3Mes), 2.13 (s,

12H, o-CH3Mes), 1.67 (m, 2H, 8-CH2), 1.57 (m, 2H, 7-CH2).

13C{1H} NMR (126 MHz, dichloromethane-d2, 299 K): δ 156.5 (br, 2-C), 148.0 (dm, 1JFC~

240 Hz, C6F5), 138.2 (dm, 146.5 (d, 4JPC = 3.1 Hz, 4-CH), 143.6 (d, 4JPC = 2.9 Hz, p-Mes), 143.2

(br d, 2JPC = 10.8 Hz, o-Mes), 142.3 (d, J = 0.9 Hz, i-Ph), 138.2 (d, 2JPC = 16.6 Hz, 10-C), 138.2

(dm, 1JFC~ 240 Hz, C6F5), 137.2 (dm, 1JFC~ 250 Hz, C6F5), 134.7 (d, 3JPC = 12.2 Hz, 5-C), 133.3

(m, 3-CH), 132.7 (d, 3JPC = 11.6 Hz, m-Mes), 129.5 (o-Ph), 128.4 (m-Ph), 128.3 (d, 1JPC =

100.5 Hz, 1-C), 127.5 (br, i-C6F5), 127.4 (p-Ph), 122.2 (d, 1JPC = 87.4 Hz, i-Mes), 30.3 (d, 3JPC

= 5.6 Hz, 9-CH2), 29.0 (d, 4JPC = 1.8 Hz, 6-CH2), 23.5 (br d, 3JPC = 3.6 Hz, o-CH3Mes), 23.0 (8-

CH2), 22.9 (7-CH2), 21.2 (d, J = 1.5 Hz, p-CH3Mes).



19F NMR (470 MHz, dichloromethane-d2, 299 K): δ -131.7 (br, 2F, o-C6F5), -161.2 (t, 3JFF =

20.3 Hz, 1F, p-C6F5), -165.4 (m, 2F, m-C6F5)[19Fmp = 4.2].

S62



S63




S64

Crystals suitable for the X-ray crystal structure analysis were obtained by slow evaporation a

solution of compound 22 in dichloromethane at room temperature:

X-ray crystal structure analysis of compound 22: formula C46H37BF10NOP, M = 851.55,

colourless crystal, 0.20 x 0.12 x 0.06 mm, a = 17.1332(2), b = 14.0711(2), c = 17.4447(3) Å, β

= 106.398(1)°, V = 4034.5(1) Å3, ρcalc = 1.402 gcm-3, μ = 0.152 mm-1, empirical absorption







S65

3 Solid State NMR Data

Experimental

Solid State NMR measurements were carried out on a BRUKER Avance III 300 spectrometer (magnetic

field strength of 7.05 T). Magic angle spinning was used in 4mm NMR double and triple resonance

probes. For 11B {1H}MAS NMR experiments a short duration pulse of 0.5-1 µs was used corresponding

approximately to a 30° flip angle to achieve uniform excitation. A spinning speed of 12.0 kHz and

relaxation delays of 20-80 s were used. Chemical shifts are reported relative to an external sample of

BF3•Et2O. 31P{1H} CPMAS NMR spectra were obtained at 12.5 kHz spinning rate using proton π/2-

pulses between 5 and 7 µs, a contact time of 3 to 5 ms with a ramp (90-100% of the maximum power

on the 1H channel). The relaxation delay was 5-15 s. Spectra were externally referenced to 85% H3PO4.

TPPM-15 proton decoupling was conducted during acquisition of 11B and 31P spectra with pulses of

about 5.5-8 µs length, corresponding to 10/12 π-pulses. Spectral deconvolution was done with DMFIT

software (version 2011).[1]

S66

Figure S78: Experimental (top line) and simulated (bottom line) 11B MAS spectra of acyclic to cyclic to aromatic FLP (7a-4a-8a and 10a-11-12) and FLP-H2 adduct 14 measured at a field of 7.05 T and a spinning

speed of 12 kHz. Grey lines show simulated sub-spectra. Crosses mark impurities of the samples.

20 10 0 -10 -20 -30

7a

+

+

4a

8a

(11

B)/ppm

10a

+

11

12

+14

S67

Table S1: Experimental 11B chemical shift and nuclear electric quadrupole coupling parameters obtained via deconvolution of MAS spectra (Figure S78).

Comp. 𝛅𝑪𝑺𝒊𝒔𝒐/ppm CQ/MHz ηQ

7a 2.0 1.95 0.30

4a 6.0/2.8 2.05/1.92 0.35

8a 9.3 2.15 0.24

10a 1.6 1.86 0.30

11 8.8 2.28 0.35

12 4.7 1.92 0.32

14 -21.8 ca. 0.5MHz ---

Figure S79: Experimental (top line) and simulated (bottom line) 31P CPMAS spectra of acyclic to cyclic to aromatic FLP (7a-4a-8a and 10a-11-12) and FLP-H2 adduct 14 measured at a field strength of 7.05 T and a spinning speed of 12.5 kHz using a 5 ms contact pulse for compounds 4a-12 and a 3 ms contact pulse for

compound 14. Grey lines show simulated sub-spectra for the 11B and 10B isotopologues. Crosses mark impurities of the samples.

20 15 10 5 -30 -35

+

7a

4a

+

+

+8a

(31

P)/ppm

10a

11

12

14

S68

Table S2 : Experimental 31P chemical shift and J-coupling constants obtained via deconvolution of CPMAS spectra (Figure S79).

Literature:

[1] D. Massiot, F. Fayon, M. Capron, I. King, S. Le Calvé, B. Alonso, J.-O. Durand, B. Bujoli,

Z. Gan and G. Hoatson, Magn. Reson. Chem. 2002, 40, 70-76.

Comp. 𝛅𝐂𝐒𝐢𝐬𝐨 / ppm J(31P-11B) / Hz

7a 17.0 33.0

4a 3.9/11.3 39.0

8a 4.4 39.0

10a 13.1 38.0

11 15.3 37.0

12 7.8 44.0

15 -34.3 ---

S69

4 EPR Data

The EPR measurements were performed in quartz tubes. Solution EPR spectra were recorded

on a JEOL continuous wave spectrometer JES-FA200 equipped with an X-band Gunn

oscillator bridge and a cylindrical mode cavity. For all samples, a modulation frequency of 100

kHz was employed. All spectra were obtained from freshly prepared fluorobenzene solutions

(0.005 M) at 298 K.

Spectral simulation was performed using the program QCMP 136 by Prof. Dr. Frank Neese

from the Quantum Chemistry Program Exchange as used by Neese et al. in J. Am. Chem.

Soc. 1996, 118, 8692-8699. The fittings were performed by the “chi by eye” approach. Collinear

g and A tensors were used. Coupling to 10B (I = 3; 19.9% abundant) was neglected in all

simulations.

Figure S80: X-band EPR spectrum and simulation for compound 19 (fluorobenzene, RT): 8.986159 GHz,

ModWidth = 0.1 mT, Power = 1.0 mW, time constant = 0.1 s. Simulation (Gaussian lineshape with 1.3 G

linebroadening) gives giso = 2.0053, A(14N) = 22.2 MHz, A(31P) = 49.6 MHz, A(11B) = 9.5 MHz

3160 3170 3180 3190 3200 3210 3220 3230 3240

Magnetic Field (Gauss)

Sim

Exp

S70

Figure S81: X-band EPR spectrum and simulation for compound 21 (fluorobenzene, RT): 8.989816 GHz,

ModWidth = 0.1 mT, Power = 1.0 mW, time constant = 0.03 s. Simulation (Gaussian lineshape with 1.2 G

linebroadening) gives giso = 2.0052, A(14N) = 23.3 MHz, A(31P) = 48.9 MHz, A(11B) = 10.0 MHz

3160 3170 3180 3190 3200 3210 3220 3230 3240Magnetic Field (Gauss)

Sim

Exp

Date post:	14-Jul-2020
Category:	Documents
Upload:	others
View:	2 times
Download:	0 times

Thomas Özgün, Guo-Qiang Chen, Constantin G. Daniliuc ... · The reaction mixture was warmed to r....

Documents