G. Erker et al.
160 MHz; 31P, 202 MHz; 19F, 470 MHz), Varian UNITY plus NMR spec-
trometer (1H, 600 MHz; 13C, 151 MHz; 11B, 192 MHz; 31P, 242 MHz; 19F,
564 MHz). Assignments of the resonances were supported by 2D experi-
ments and chemical shift calculations. 11B NMR spectra were referenced
to an external Et2O·BF3 (neat) sample; 31P NMR spectra were referenced
to an external H3PO4 sample (85% solution in water); 19F NMR spectra
were referenced to an external CFCl3 (neat) sample. X-ray crystal struc-
ture analyses: Data sets were collected with a Nonius KappaCCD diffrac-
tometer. Programs used: data collection COLLECT (Nonius B.V., 1998),
data reduction Denzo-SMN[16] and PLATON,[17] absorption correction
Denzo,[18] structure solution SHELXS-97,[19] structure refinement
SHELXL-97,[20] graphics SCHAKAL.[21] CCDC-781886 (4), CCDC-
781887 (6), and CCDC-781888 (5) contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge
ac.uk/data_request/cif.
slow evaporation of a heptane solution at ꢀ308C. 1H NMR (500 MHz,
298 K, [D8]toluene): d=6.48 (br, 2H, m-MesA), 6.43 (br, 2H, m-MesB),
3
3
2.95 (dt, JHH =14.4 Hz, JHH =3.6 Hz, 1H, CHP), 2.35, 1.40 (each m, each
1H, 5-H), 2.10 (br, 6H, o-CH3Mes(B)), 1.95, 0.99 (each m, each 1H, 2-H),
Mes(A)
1.94 (m, 1H, CHP), 1.92 (s, 6H, p-CH3
and p-CH3Mes(B)), 1.91 (br,
6H, o-CH3Mes(A)), 1.57, 0.97 (each m, each 1H, 4-H), 1.48, 1.11 ppm (each
m, each 1H, 3-H); 13C{1H} NMR (126 MHz, 298 K, [D8]toluene): d=
147.5 (dm, JCF ꢂ242 Hz, C6F5), 143.8 (br d, 2JPC =6.5 Hz, o-MesA(t)),
1
141.0 (br d, 2JPC =8.2 Hz, o-MesB(t)), 140.8 (d, 4JPC =2.3 Hz, p-MesA(t)),
140.3 (dm, JCF ꢂ252 Hz, C6F5), 140.1 (d, 4JPC =2.5 Hz, p-MesB(t)), 137.6
1
(dm, JCF ꢂ252 Hz, C6F5), 131.1 (br d, 3JPC =7.8 Hz, m-MesA), 130.5 (d,
1
3JPC =7.8 Hz, m-MesB), 130.1 (br d, 1JPC =12.1 Hz, i-MesB), 124.9 (d,
1JPC =26.6 Hz, i-MesA), 119.8 (br, i-C6F5), 46.0 (d, 1JPC =27.0 Hz, CHP),
37.6 (br, CHB), 32.9 (d, 3JPC =49.0 Hz, C-5), 29.9 (d, 2JPC =7.0 Hz, C-2),
27.2 (C-4), 27.0 (d, 3JPC =8.4 Hz, C-3), 24.3 (br, o-CH3Mes(A)), 22.7 (br, o-
CH3Mes(B)), 20.7 (d, 5JPC =1.1 Hz, p-CH3Mes(B)), 20.5 ppm (d, 5JPC =1.1 Hz,
p-CH3Mes(A)) [(t): tentative assignment]; 31P{1H} NMR (202 MHz, 298 K,
[D8]toluene): d=23.5 ppm (m, n1/2 ꢂ30 Hz); 11B{1H} NMR (160 MHz,
298 K, [D8]toluene): d=12.6 ppm (n1/2 ꢂ670 Hz); 19F NMR (470 MHz,
298 K, [D8]toluene): d=ꢀ127.5 (br, 2F, o-C6F5), ꢀ156.9 (1F, p-C6F5),
Synthesis of 4: DiACHTUNGTRENNUNG(mesityl)cyclohexenylphosphine (53 mg, 0.15 mmol)
and bis(pentafluorophenyl)borane (52 mg, 0.15 mmol) were mixed in
heptane (2 mL). The mixture was stirred for 30 min at room temperature
until a clear transparent yellow solution was obtained. The resulting
yellow solution was transferred into a Schlenk flask, which was charged
with 1.5 bar of dihydrogen at ꢀ208C and then placed into a freezer at
ꢀ208C and kept there for 2 h. The product precipitated as colorless crys-
tals. Heptane was removed by using a syringe, and the precipitate was
dried in vacuo at ꢀ208C to give the product 4 as a white solid (74 mg,
71%). At 258C, compound 4 was unstable in solution and decomposed.
Crystals suitable for X-ray crystal structure analysis were obtained from
a heptane solution at ꢀ208C. 1H NMR (500 MHz, 193 K, [D8]toluene)
ꢀ163.6 ppm (2F, m-C6F5); elemental analysis calcd (%) for C36H32PBF10
:
C 62.09, H 4.63; found: C 63.02, H 4.02.
X-ray crystal structure analysis of 5: Formula C36H32BF10P, Mr =696.40,
colorless crystal 0.15ꢅ0.10ꢅ0.07 mm, a=18.9773(7), b=17.4327(6), c=
22.5078(8) ꢁ, b=91.729(2)8, V=7442.8(5) ꢁ3, 1calcd =1.243 gcmꢀ3
, m=
1.307 mmꢀ1, empirical absorption correction (0.828ꢃTꢃ0.914), Z=8,
monoclinic, space group P21/n (no. 14), l=1.54178 ꢁ, T=223(2) K, w
and f scans, 53357 reflections collected (ꢁh, ꢁk, ꢁl), [(sinq)/l]=
0.60 ꢁꢀ1, 13044 independent (Rint =0.124) and 7343 observed reflections
[Iꢄ2s(I)], 877 refined parameters, R=0.072, wR2 =0.208, max. (min.) re-
sidual electron density 0.24 (ꢀ0.36) eꢁꢀ3, hydrogen atoms calculated and
refined as riding atoms, disordered solvent molecules couldn’t be as-
signed, therefore SQUEEZE was used.
1
[all signals are broad, 4:heptane ca. 10:6]: d=7.94 (br d, JPH ꢂ496 Hz,
1H, PH), 6.33 (br s, 1H, m-MesA), 6.23 (br s, 1H, m-MesB), 6.12 (br s,
1H, m’-MesA), 6.06 (br s, 1H, m’-MesB), 3.49 (br, 1H, CHP), 3.35 (br,
1H, BH), 2.41, 2.06, 1.67, 1.49 (each br s, each 3H, o-CH3Mes), 2.14, 1.42
(each br, each 1H, CH2Cy), 1.82 (br s, 6H, p-CH3Mes(A), p-CH3Mes(B)), 1.74
(br, 1H, CHB), 1.63, 1.17 (each br, each 1H, CH2Cy), 1.54, 1.16 (each br,
each 2H, CH2Cy), 1.41, 1.22 ppm (each br, each 2H, CH2Cy); 13C{1H}
NMR (126 MHz, 193 K, [D8]toluene) [all signals are broad, key reso-
Synthesis of 6: DiACTHUNTGRNEUNG(mesityl)cyclohexenylphosphine (100 mg, 0.28 mmol)
and bis(pentafluorophenyl)borane (99 mg, 0.28 mmol) were mixed in
pentane (8 mL). The mixture was stirred for 15 min. After addition of
phenyl isocyanate (155 mL, 1.4 mmol), the reaction mixture was stirred
for 3.5 h. The resulting white precipitate was isolated by cannula filtra-
tion from the suspension and washed three times with pentane (3 mL).
Removal of all volatiles in vacuo yielded the product 6 as a white
powder (170 mg, 74%). Crystals suitable for the X-ray crystal structure
analysis were obtained by gas diffusion of heptane into a benzene solu-
tion of 6. 1H NMR (600 MHz, 298 K, CD2Cl2): d=7.30 (m, 2H, o-Ph),
7.22 (m, 2H, m-Ph), 7.07 (m, 1H, p-Ph), 7.05 (d, 4JPH =4.2 Hz, 2H, m-
MesA), 6.97 (d, 4JPH =4.1 Hz, 2H, m-MesB), 3.54 (m, 1H, CHP), 2.44 (s,
6H, o-CH3Mes(B)), 2.36 (s, 3H, p-CH3Mes(A)), 2.32 (s, 3H, p-CH3Mes(B)), 2.20
(br s, 6H, o-CH3Mes(A)), 2.15, 1.58 (each br m, each 1H, 2-H), 1.84, 1.11
(each br m, each 1H, 5-H), 1.76, 1.27 (each m, each 1H, 3-H), 1.70 (br
m, 1H, CHB), 1.62, 1.11 ppm (each m, each 1H, 4-H); 13C{1H} NMR
(151 MHz, 298 K, CD2Cl2): d=150.3 (d, 1JPC =122.1 Hz, CN), 148.3 (dm,
ACHTUNGTRENNUNG
nances are listed using the ghsqc experiment]: d=131.8 (m-MesA), 131.6
1
(m’-MesB), 130.9 (m’-MesA, m-MesB), 42.7 (br d, JPC ꢂ41 Hz, CHP), 36.2
(br, CHB), 34.1, 30.4, 27.9, 27.1 (CH2Cy), 23.7, 22.5, 21.3, 20.6 (br, o-
CH3Mes), 20.7 ppm (br, p-CH3Mes(A), p-CH3Mes(B)); 11B{1H} NMR (160 MHz,
193 K, [D8]toluene): d=ꢀ19.7 ppm (n1/2 ꢂ130 Hz); 11B NMR (160 MHz,
1
193 K, [D8]toluene): d=ꢀ19.7 ppm (d, JBH ꢂ70 Hz); 31P{1H} NMR
(202 MHz, 193 K, [D8]toluene) d=ꢀ4.5 (85%, n1/2 ꢂ40 Hz), [ꢀ13.6 (un-
identified product, 15%, n1/2 ꢂ70 Hz), ꢀ95.0 ppm (traces of Mes2PH, n1/2
ꢂ5 Hz)]; 31P NMR (202 MHz, 193 K, [D8]toluene): d=ꢀ4.5 (85%, d,
1JPH =496 Hz), [ꢀ13.6 (unidentified product, 15%, d, 1JPH =496 Hz),
ꢀ95.0 ppm (traces of Mes2PH, d, 1JPH =235 Hz)]; 19F NMR (470 MHz,
193 K, [D8]toluene): d=ꢀ129.4 (br, o-C6F5), ꢀ130.3 (br, o-C6F5), ꢀ161.3
(br, p-C6F5), ꢀ164.4 ppm (br, m-C6F5); elemental analysis calcd (%) for
C36H34BF10P·0.6C7H16: C 63.65, H 5.79; found: C 63.43, H 5.67.
1
3
X-ray crystal structure analysis of 4: Formula C36H34BF10P, Mr =698.41,
colorless crystal 0.20ꢅ0.15ꢅ0.05 mm, a=11.0288(9), b=12.2541(8), c=
1JCF ꢂ238 Hz, C6F5), 147.6 (dm, JCF ꢂ231 Hz, C6F5), 145.9 (d, JPC
=
21.8 Hz, i-Ph), 144.7 (d, 2JPC =9.1 Hz, o-MesA), 144.1 (d, 4JPC =2.9 Hz, p-
15.3222(10) ꢁ,
a=68.595(3),
b=89.107(3),
g=85.844(6)8,
empirical absorption
¯
V=
MesA), 144.0 (d, 4JPC =3.0 Hz, p-MesB), 143.9 (br, o-MesB), 139.2 (dm,
1922.7(2) ꢁ3, 1calcd =1.206 gcmꢀ3
,
m=1.265 mmꢀ1
,
1JCF ꢂ250 Hz, 2ꢅC6F5), 137.2 (dm, JCF ꢂ248 Hz, 2ꢅC6F5), 132.6 (d,
1
correction (0.786ꢃTꢃ0.940), Z=2, triclinic, space group P1 (no. 2), l=
1.54178 ꢁ, T=223(2) K, w and f scans, 22913 reflections collected (ꢁh,
ꢁk, ꢁl), [(sinq)/l]=0.60 ꢁꢀ1, 6451 independent (Rint =0.087) and 4401
observed reflections [Iꢄ2s(I)], 445 refined parameters, R=0.070, wR2 =
0.207, max. (min.) residual electron density 0.24 (ꢀ0.25) eꢁꢀ3, hydrogen
atoms at P and B from difference Fourier calculations, others calculated
and refined as riding atoms, disordered solvent molecules couldn’t be as-
signed, therefore SQUEEZE was used.
3JPC =7.0 Hz, m-MesA), 132.5 (d, 3JPC =7.5 Hz, m-MesB), 128.5 (m-Ph),
1
125.7 (p-Ph), 125.1 (o-Ph), 122.8 (br, 2ꢅi-C6F5), 121.6 (d, JPC =73.4 Hz, i-
MesB), 115.2 (d, JPC =74.1 Hz, i-MesA), 42.5 (d, JPC =34.3 Hz, CHP), 30.0
(d, 3JPC =13.1 Hz, C-5), 29.5 (d, 2JPC =4.0 Hz, C-2), 29.4 (br, CHB), 27.0
(C-4), 26.8 (d, 3JPC =13.2 Hz, C-3), 24.6 (d, 3JPC =4.2 Hz, o-CH3Mes(A)),
24.5 (br, o-CH3Mes(B)), 21.1 (p-CH3Mes(A)), 20.9 ppm (p-CH3Mes(B)); 11B{1H}
NMR (160 MHz, 298 K, CD2Cl2): d=1.4 ppm (n1/2 ꢂ340 Hz); 31P{1H}
NMR (202 MHz, 298 K, CD2Cl2): d=8.5 ppm (n1/2 ꢂ25 Hz); 19F NMR
(470 MHz, 298 K, CD2Cl2): d=ꢀ130.0, ꢀ133.8 (each br, each 2F, o-C6F5),
ꢀ160.9 (1F, p-C6F5A), ꢀ161.0 (1F, p-C6F5B), ꢀ165.0 (2F, m-C6F5A),
ꢀ165.7 ppm (2F, m-C6F5B); elemental analysis calcd (%) for
C43H37BF10NOP: C 63.33, H 4.57, N 1.72; found: C 62.60, H 4.49, N 1.77.
1
1
Synthesis of 5: Bis(pentafluorophenyl)borane (98 mg, 0.28 mmol) was
added to
a solution of diACTHUNTGNRUEGN(mesityl)cyclohexenylphosphine (100 mg,
0.28 mmol) in [D6]benzene (1 mL). After the reaction mixture had been
stirred for 30 min at room temperature, all volatiles were evaporated in
vacuo to give the product as a bright yellow solid (190 mg, 100%). Crys-
tals suitable for the X-ray crystal structure analysis were obtained by a
X-ray crystal structure analysis of 6: Formula C43H37BF10NOP·1.5C6H6,
Mr =932.68, colorless crystal 0.40ꢅ0.35ꢅ0.15 mm, a=11.6750(4), b=
14072
ꢄ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 14069 – 14073