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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
Synthesis of compound 12 ................................................................................................ 24
Synthesis of compound 13 ................................................................................................ 31
Synthesis of compound 14 ................................................................................................ 36
Generation of compound 14-D2 ........................................................................................ 40
Synthesis of compound 17 ................................................................................................ 44
Synthesis of compound 18 ................................................................................................ 49
Synthesis of compound 19 ................................................................................................ 53
Synthesis of compound 20 ................................................................................................ 55
Synthesis of compound 21 ................................................................................................ 59
Synthesis of compound 22 ................................................................................................ 61
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.
Anal. Calc. for C44H42BF10P: C: 65.85; H: 5.27. Found: C: 65.79; H: 5.21.
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
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): 567 Hz
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
Synthesis of compound 11
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.
Anal. Calc. for C46H38BF10P: C: 67.17; H: 4.66. Found: C: 66.79; H: 5.02.
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’):
1H NMR (500 MHz, dichloromethane-d2, 213 K): δ 7.20 (m, 2H, m-Ph), 7.16 (m, 2H, o-Ph),
7.14 (m, 1H, p-Ph), 7.01 (br, 1H, m-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, 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 -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
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): 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)
Synthesis of compound 12
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.
Anal. Calc. for C46H36BF10P: C: 67.33; H: 4.42. Found: C: 67.65; H: 5.17.
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].
31P{1H} NMR (202 MHz, dichloromethane-d2, 299 K): δ 5.8 (1/2 ~ 36 Hz).
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].
31P{1H} NMR (202 MHz, dichloromethane-d2, 193 K): δ 4.1 (1/2 ~ 40 Hz).
11B{1H} NMR (160 MHz, dichloromethane-d2, 193 K): δ 2.0 (broad).
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]
Figure S29: 19F NMR (470 MHz, dichloromethane-d2, 193 K) spectrum of compound 12
S28
Figure S30: 31P{1H} NMR (202 MHz, dichloromethane-d2, 193 K) spectrum of compound 12
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
G‡[Tc, (T)] = RTc(22.96 + ln(Tc/)) [J/mol]
Tc= coalescence temperature [K]: 243 K (19F, p-BC6F5)
= chemical shift difference [Hz] (19F, p-BC6F5, 193 K): 426 Hz
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
Crystals suitable for the X-ray crystal structure analysis were obtained by slow diffusion of
pentane into a solution of compound 12 in dichloromethane at -35 °C:
X-ray crystal structure analysis of compound 12: formula 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.
Figure S34: X-ray crystal structure of compound 12 (thermal ellipsoids are shown at the 30% probability level)
S31
Synthesis of compound 13
Scheme S6
Phenylacetylene (12.4 mg, 122 µmol, 1.0 eq) was added dropwise to a solution of
compound 11 (100 mg, 122 µmol, 1.0 eq) in toluene (4 mL) at ambient temperature and then
the reaction mixture was stirred for 16 hours at 80 °C. Subsequently all volatiles were removed
in vacuo and the resulting yellow oil suspended in pentane (2 mL). Then the reaction
suspension was dried in vacuo and the resulting solid was washed with pentane (3 x 2 mL).
After drying in vacuo, compound 13 was obtained as a white solid (43.8 mg, 47.4 μmol; 39%).
IR (KBr): ṽ [cm-1] = 3060 (w), 3027 (w), 2931 (w), 2361 (w) 1945 (w), 1747 (w), 1639 (w), 1603
(w), 1547 (w), 1511 (m), 1452 (s), 1382 (w), 1296 (w), 1269 (m), 1248 (m), 1154 (w), 1083 (s),
1033 (w), 966 (s), 910 (w), 854 (w), 784 (w), 757 (m), 738 (w), 696 (m), 645 (m), 605 (w), 558
(w), 490 (w), 421 (w).
M.p. 182 °C.
Anal. Calc. for C54H44BF10P: C: 70.14; H: 4.80. Found: C: 68.60; H: 4.56.
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 ).
11B{1H} NMR (160 MHz, dichloromethane-d2, 253 K): δ −17.7 (1/2 ~ 50 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].
Figure S35: 1H NMR (500 MHz, dichloromethane-d2, 253 K) spectrum of compound 13
S33
Figure S36: 13C NMR (126 MHz, dichloromethane-d2, 253 K) spectrum of compound 13
Figure S37: 19F NMR (470 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
Crystals suitable for the X-ray crystal structure analysis were obtained from a dichloromethane
solution of compound 13 at -35 °C:
X-ray crystal structure analysis of compound 13: A colorless prism-like specimen of
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,
completeness = 99.9%, Rint = 5.56%, Rsig = 4.69%) and 8954 (87.49%) were greater than
2σ(F2). The final cell constants of a = 14.2250(7) Å, b = 11.9311(5) Å, c = 15.3276(7) Å, β =
105.716(2)°, volume = 2504.1(2) Å3, are based upon the refinement of the XYZ-centroids of
9863 reflections above 20 σ(I) with 4.573° < 2θ < 52.62°. Data were corrected for absorption
effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent
transmission was 0.923. The calculated minimum and maximum transmission coefficients
(based on crystal size) are 0.9740 and 0.9760. The structure was solved and refined using the
Bruker SHELXTL Software Package, using the space group P 1 n 1, with Z = 2 for the formula
unit, 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-.
Figure S40: X-ray crystal structure of compound 13 (thermal ellipsoids are shown at the 50% probability level)
S36
Synthesis of compound 14
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.
Anal. Calc. for C46H38BF10P: C: 67.17; H: 4.66. Found: C: 67.36; H: 5.28.
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)
11B{1H} NMR (192 MHz, dichloromethane-d2, 299 K): δ −20.8 (1/2 ~ 55 Hz)
19F NMR (564 MHz, dichloromethane-d2, 299 K): δ -130.9 (m, 2F, o), -163.2 (t, 3JFF = 20.1 Hz,
1F, p), -166.9 (m, 2F, m)(C6F5)[19Fmp = 3.7], -133.0 (m, 2F, o), -162.7 (t, 3JFF = 20.1 Hz, 1F,
p), -166.3 (m, 2F, m)(C6F5)[19Fmp = 3.6].
Figure S41: 1H NMR (600 MHz, dichloromethane-d2, 299 K) spectrum of compound 14
S38
Figure S42: 13C{1H} NMR (151 MHz, dichloromethane-d2, 299 K) spectrum of compound 14
Figure S43: 19F NMR (564 MHz, dichloromethane-d2, 299 K) spectrum of compound 14
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
Figure S46: X-ray crystal structure of compound 14 (thermal ellipsoids are shown at the 30% probability level)
Generation of compound 14-D2
Scheme S8
A yellow solution of compound 12 (20.0 mg, 24.4 mol, 1.0 eq) in 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)
11B{1H} 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
Synthesis of compound 17
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]
31P{1H} NMR (243 MHz, dichloromethane-d2, 299 K): δ 15.9 (1/2 ~ 4 Hz).
11B{1H} NMR (192 MHz, dichloromethane-d2, 299 K): δ 0.8 (1/2 ~ 330 Hz).
19F NMR (564 MHz, dichloromethane-d2, 299 K): δ -127.2 (m, o), -137.6 (m, o’), -160.9 (t, 3JFF
= 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:
31P{1H} NMR (243 MHz, dichloromethane-d2, 299 K): δ 16.5 (1/2 ~ 30 Hz).
11B{1H} NMR (192 MHz, dichloromethane-d2, 299 K): δ 0.8 (1/2 ~ 330 Hz).
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
Figure S52: 1H NMR (600 MHz, dichloromethane-d2, 299 K) spectrum of compound 17
Figure S53: 13C{1H} NMR (151 MHz, dichloromethane-d2, 299 K) spectrum of compound 17
S47
Figure S54: 19F NMR (564 MHz, dichloromethane-d2, 299 K) spectrum of compound 17
Figure S55: 31P{1H} NMR (243 MHz, dichloromethane-d2, 299 K) spectrum of compound 17
Figure S56: 11B{1H} NMR (192 MHz, dichloromethane-d2, 299 K) spectrum of compound 17
Crystals suitable for the X-ray crystal structure analysis were obtained from a dichloromethane
solution of compound 17 at room temperature:
X-ray crystal structure analysis of compound 17: A colorless prism-like specimen of
C52H44BF10O4P, approximate dimensions 0.110 mm x 0.137 mm x 0.206 mm, was used for the
X-ray crystallographic analysis. The X-ray intensity data were measured. A total of 748 frames
S48
were collected. The total exposure time was 8.31 hours. The frames were integrated with the
Bruker SAINT software package using a narrow-frame algorithm. The integration of the data
using a monoclinic unit cell yielded a total of 8271 reflections to a maximum θ angle of 25.03°
(0.84 Å resolution), of which 8271 were independent (average redundancy 1.000,
completeness = 99.8%, Rint = 8.35%, Rsig = 3.22%) and 6534 (79.00%) were greater than
2σ(F2). The final cell constants of a = 14.9814(7) Å, b = 16.7671(7) Å, c = 19.0481(8) Å, β =
100.8210(10)°, volume = 4699.7(4) Å3, are based upon the refinement of the XYZ-centroids of
9841 reflections above 20 σ(I) with 4.858° < 2θ < 54.47°. Data were corrected for absorption
effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent
transmission was 0.959. The calculated minimum and maximum transmission coefficients
(based on crystal size) are 0.9710 and 0.9840. 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, 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
synthesis was 0.378 e-/Å3 and the largest hole was -0.345 e-/Å3 with an RMS deviation of 0.054
e-/Å3. On the basis of the final model, the calculated density was 1.363 g/cm3 and F(000),
1992 e-.
Figure S57: X-ray crystal structure of compound 17 (thermal ellipsoids are shown at the 50% probability level)
S49
Synthesis of compound 18
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]
31P{1H} NMR (202 MHz, dichloromethane-d2, 213 K): δ 15.1 (1/2 ~ 5 Hz).
11B{1H} NMR (160 MHz, dichloromethane-d2, 299 K): δ 1.1 (1/2 ~ 350 Hz).
19F NMR (470 MHz, dichloromethane-d2, 299 K): δ -128.5 (m, o), -136.8 (m, o’), -160.0 (t, 3JFF
= 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].
Figure S58: 1H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of compound 18
S51
Figure S59: 13C{1H} NMR (126 MHz, dichloromethane-d2, 299 K) spectrum of compound 18
Figure S60: 19F NMR (470 MHz, dichloromethane-d2, 299 K) spectrum of compound 18
Figure S61: 31P{1H} NMR (202 MHz, dichloromethane-d2, 299 K) spectrum of compound 18
S52
Figure S62: 11B{1H} NMR (160 MHz, dichloromethane-d2, 299 K) spectrum of compound 18
Crystals suitable for the X-ray crystal structure analysis were obtained from a dichloromethane
solution of compound 18 at -35 °C:
X-ray crystal structure analysis of compound 18: A colorless plate-like specimen of
C52H42BF10O4P, approximate dimensions 0.020 mm x 0.080 mm x 0.220 mm, was used for the
X-ray crystallographic analysis. The X-ray intensity data were measured. A total of 1592 frames
were collected. The total exposure time was 20.62 hours. The frames were integrated with the
Bruker SAINT software package using a wide-frame algorithm. The integration of the data
using a monoclinic unit cell yielded a total of 8235 reflections to a maximum θ angle of 66.59°
(0.84 Å resolution), of which 8235 were independent (average redundancy 1.000,
completeness = 99.8%, Rint = 9.30%, Rsig = 5.39%) and 6008 (72.96%) were greater than
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
9144 reflections above 20 σ(I) with 7.138° < 2θ < 133.0°. Data were corrected for absorption
effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent
transmission was 0.839. The calculated minimum and maximum transmission coefficients
(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
Figure S63: X-ray crystal structure of compound 18 (thermal ellipsoids are shown at the 50% probability level)
Synthesis of compound 19
Scheme S11
A solution of compound 11 (200.0 mg, 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.
Crystals suitable for the X-ray crystal structure analysis were obtained by slow diffusion of
pentane into a solution of compound 19 in dichloromethane at -35 °C:
X-ray crystal structure analysis of compound 19: formula 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.
Figure S64: X-ray crystal structure of compound 19 (thermal ellipsoids are shown at the 30% probability level)
S55
Synthesis of compound 20
Scheme S12
1,8-Cyclohexadiene (131.6 mg, 1.64 mmol, 10.0 eq) was added to a turquoise solution of
compound 19 (140.0 mg, 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.
Anal. Calc. for C46H39BF10PNO: C: 64.73; H: 4.61; N: 1.64. Found: C: 64.71; H: 4.50; N: 1.58.
1H NMR (500 MHz, dichloromethane-d2, 299 K): δ 7.33 (m, 2H, m-Ph), 7.29 (m, 2H, o-Ph),
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]
31P{1H} NMR (202 MHz, dichloromethane-d2, 299 K): δ 28.7 (1/2 ~ 25 Hz).
11B{1H} NMR (160 MHz, dichloromethane-d2, 299 K): δ −6.6 (1/2 ~ 130 Hz)
19F NMR (470 MHz, dichloromethane-d2, 299 K): δ -128.7 (m, 2F, o), -161.5 (t, 3JFF = 20.3 Hz,
1F, p), -165.9 (m, 2F, m)(C6F5)[19Fmp = 4.4], -136.8 (m, 2F, o), -162.6 (t, 3JFF = 20.3 Hz, 1F,
p), -165.3 (m, 2F, m)(C6F5)[19Fmp = 2.7].
Figure S65: 1H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of compound 20
S57
Figure S66: 13C{1H} NMR (126 MHz, dichloromethane-d2, 299 K) spectrum of compound 20
Figure S67: 19F NMR (470 MHz, dichloromethane-d2, 299 K) spectrum of compound 20
Figure S68 31P{1H} NMR (202 MHz, dichloromethane-d2, 299 K) spectrum of compound 20
S58
Figure S69: 11B{1H} NMR (160 MHz, dichloromethane-d2, 299 K) spectrum of compound 20
Crystals suitable for the X-ray crystal structure analysis were obtained by slow evaporation
from a dichloromethane solution of compound 20:
X-ray crystal structure analysis of compound 20: A colorless prism-like specimen of
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,
completeness = 99.2%, Rint = 7.46%, Rsig = 3.97%) and 5503 (77.91%) were greater than
2σ(F2). The final cell constants of a = 12.5817(5) Å, b = 15.0138(6) Å, c = 22.1390(9) Å, β =
105.279(2)°, volume = 4034.2(3) Å3, are based upon the refinement of the XYZ-centroids of
9971 reflections above 20 σ(I) with 7.197° < 2θ < 135.7°. Data were corrected for absorption
effects using the multi-scan method (SADABS). The ratio of minimum to maximum apparent
transmission was 0.841. The calculated minimum and maximum transmission coefficients
(based on crystal size) are 0.7750 and 0.9000. 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, 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
synthesis was 0.744 e-/Å3 and the largest hole was -0.363 e-/Å3 with an RMS deviation of 0.060
e-/Å3. On the basis of the final model, the calculated density was 1.405 g/cm3 and F(000),
1760 e-.
S59
Figure S70: X-ray crystal structure of compound 20 (thermal ellipsoids are shown at the 50% probability level)
Synthesis of compound 21
Scheme S13
A solution of compound 12 (100.0 mg, 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.
Anal. Calc. for C46H36BF10PNO: C: 64.96; H: 4.27; N: 1.65. Found: C: 65.34; H: 4.28; N: 1.31.
Crystals suitable for the X-ray crystal structure analysis were obtained by slow diffusion of
pentane into a solution of compound 21 in dichloromethane at -35 °C:
X-ray crystal structure analysis of compound 21: formula 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
correction (0.976 ≤ T ≤ 0.984), Z = 4, monoclinic, space group P21/n (No. 14), λ = 0.71073 Å,
T = 223(2) K, ω and φ scans, 23571 reflections collected (±h, ±k, ±l), 6794 independent (Rint =
0.053) and 5010 observed reflections [I>2σ(I)], 639 refined parameters, R = 0.066, wR2 =
0.139, max. (min.) residual electron density 0.31 (-0.29) e.Å-3, hydrogen atoms were calculated
and refined as riding atoms.
Figure S71: X-ray crystal structure of compound 21 (thermal ellipsoids are shown at the 30% probability level)
S61
Synthesis of compound 22
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.
Anal. Calc. for C46H37BF10PNO: C: 64.88; H: 4.38; N: 1.64. Found: C: 65.00; H: 4.44; N: 1.50.
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).
31P{1H} NMR (202 MHz, dichloromethane-d2, 299 K): δ 33.7 (1/2 ~ 40 Hz).
11B{1H} NMR (160 MHz, dichloromethane-d2, 299 K): δ −5.4 (1/2 ~ 150 Hz)
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
Figure S72: 1H NMR (500 MHz, dichloromethane-d2, 299 K) spectrum of compound 22
Figure S73: 13C{1H} NMR (126 MHz, dichloromethane-d2, 299 K) spectrum of compound 22
S63
Figure S74: 19F NMR (470 MHz, dichloromethane-d2, 299 K) spectrum of compound 22
Figure S75: 31P{1H} NMR (202 MHz, dichloromethane-d2, 299 K) spectrum of compound 22
Figure S76: 11B{1H} NMR (160 MHz, dichloromethane-d2, 299 K) spectrum of compound 22
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
correction (0.970 ≤ T ≤ 0.990), Z = 4, monoclinic, space group P21/n (No. 14), λ = 0.71073 Å,
T = 223(2) K, ω and φ scans, 22804 reflections collected (±h, ±k, ±l), 6988 independent (Rint =
0.058) and 4841 observed reflections [I>2σ(I)], 548 refined parameters, R = 0.070, wR2 =
0.143, max. (min.) residual electron density 0.26 (-0.32) e.Å-3, hydrogen atoms were calculated
and refined as riding atoms.
Figure S77: X-ray crystal structure of compound 22 (thermal ellipsoids are shown at the 30% probability level)
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