Organometallics
Article
CD2Cl2, 298 K): δ [ppm] = −131.2 (d, JFF = 21.8 Hz, 6F, o-C6F5),
−161.7 (t, JFF = 20.8 Hz, 3F, p-C6F5), −165.7 (m, 6F, m-C6F5). 11B
NMR (95 MHz, CD2Cl2, 298 K): −19.5 (s). 13C NMR {1H} (100
127.58 (s, Ar), 126.02 (s, Ar), 125.00 (s, Ar), 124.98 (d, Ar, JPC = 3.4
Hz), 68.14 (s, alkyne), 29.30 (s, iPr), 24.86 (s, iPr), 24.04 (s, iPr).
Anal. Calcd for C71H56AuBF15N2P: C, 58.37; H, 3.86 ; N, 1.92%.
Found: C, 58.44; H, 4.02; N, 2.08%.
MHz, CD2Cl2, 298 K): δ [ppm] = 180.5 (s, NHC), 148.4 (dm, JCF
=
243.0 Hz, C−F), 145.8 (s, NHC), 139.3 (dm, JCF = 248.0 Hz, C−F),
137.1 (dm, JCF = 248.0 Hz, C−F), 134.0 (s, NHC), 131.5 (s, NHC),
124.8 (s, NHC), 124.8 (s, NHC), 122.3 (brs., C−B), 102.4 (s), 72.0
(s), 70.2 (s), 70.0 (s), 64.3 (s), 29.3 (s), 24.4 (s), 24.1 (s). One of the
C−B could not be observed. HRMS-FAB (+) (m/z): calcd for
C57H46AuBF15FeN2, 1307.2529; found, 1307.2557.
Compound 11. B(C6F5)3 (22.1 mg, 0.043 mmol) was added to
tBu3PAu-CC-tol (22.2 mg, 0.043 mmol) dissolved in CH2Cl2 (0.6
mL) and stirred for 30 min. Slow diffusion of pentane into this
solution at −20 °C afforded the product as colorless crystals (35.2 mg,
79%). IR (thin film) νmax = 2953.9 cm−1, 2059, 1642, 1513, 1459,
1396, 1374, 1280, 1170, 1088, 1023, 978, 940, 921, 903, 821, 798, 771,
762, 742. 1H NMR (600 MHz, CD2Cl2, 298 K): δ [ppm] = 7.42 (d, J
Compound 14. To a solution of (Idipp)Au−CC-ptol (34.3 mg,
0.047 mmol) in C6D6 (1 mL) was added B(C6F5)3 (24.2 mg, 0.047
mmol). The solution was stirred for 10 min at room temperature, and
then (Idipp)Au−CC-Me (30.5 mg, 0.047 mmol) was added. The
solution was layered with pentane to afford the desired product as a
colorless solid (63.2 mg, 72%). IR (thin film) νmax = 2965.3 cm−1,
2929, 2872, 1642, 1595, 1555, 1510, 1459, 1419, 1386, 1366, 1329,
1
1273, 1215, 1182, 1087, 975, 951, 803. H NMR (500 MHz, C6D6,
298 K): δ [ppm] = 7.57 (d, J = 8.0 Hz, 2H), 7.24 (t, J = 7.8 Hz, 4H),
7.01 (d, J = 7.5 Hz, 8H), 6.77 (d, J = 7.8 Hz, 2H), 6.46 (s, 4H), 2.36
(sept., J = 6.9 Hz, 8H), 2.05 (s, 3H), 1.08 (d, J = 6.9 Hz, 24H), 1.06
(d, J = 6.9 Hz, 24H). 19F NMR (470 MHz, C6D6, 298 K): δ [ppm] =
−131.1 (d, JFF = 21.7 Hz, 6F, o-C6F5), −163.8 (t, JFF = 20.9 Hz, 3F, p-
C6F5), −166.9 (m, 6F, m-C6F5). 11B NMR (160 MHz, C6D6, 298 K): δ
[ppm] = −19.9 (s). 13C NMR {1H} (100 MHz, C6D6, 298 K): δ
[ppm] = 183.0 (s), 149.4 (dm, JCF = 239 Hz), 145.6 (s), 138.9 (dm,
JCF = 250 Hz), 137.3 (dm, JCF = 245 Hz), 133.9 (s), 132.0 (s), 131.2
(s), 128.8 (s), 128.4 (s), 128.0 (s), 124.5 (s), 123.9 (s), 115.1 (s),
110.8 (s), 28.9 (s), 24.7 (s), 23.6 (s), 21.3 (s), 6.2 (s). Carbon atoms
attached to boron could not be observed. EA (elemental analysis)
calcd (%) for C84H82Au2BF15N4: C 54.91, H 4.50%; N 3.05 Obs. C
54.43, H 4.64, N 2.84%. HRMS-ESI (+) (m/z): calcd for
[C57H75Au2N4]+, 1209.5323; found, 1209.5333. HRMS-ESI (−) (m/
z): calcd for [C27H7BF15], 627.0401; found, 627.0399.
= 7.6 Hz, 2H), 7.21 (d, J = 7.6 Hz, 2H), 2.377 (s, 3H), 1.32 (d, JPH
=
14.3 Hz, 27H). 19F NMR (470 MHz, CD2Cl2, 298 K): δ [ppm] =
−131.6 (d, JFF = 21.7 Hz, 6F, o-C6F5), −161.2 (t, JFF = 20.4 Hz, 3F, p-
C6F5), −165.9 (m, 6F, m- C6F5). 31P NMR (243 MHz, CD2Cl2, 298
K): δ [ppm] = 96.5 (s). 11B NMR (96 MHz, CD2Cl2, 298 K): δ [ppm]
= −19.5 (s). 13C NMR {1H} (150 MHz, CD2Cl2, 298 K): δ [ppm] =
148.7 (dm, JCF = 239.8 Hz), 142.0 (s), 139.7 (dm, JCF = 248.7 Hz),
137.4 (dm, JCF = 248.7 Hz), 132.5 (s), 130.2 (s), 122.1 (brs, C−B),
118.8 (s), 111.4 (q, JCB = 56 Hz, C−B), 104.5 (brs), 40.1 (d, JCP = 18.9
Hz), 32.2 (s), 21.9 (s). EA calcd (%) for C39H34AuBF15P: C 45.64, H
3.34%. Obs. C 45.25, H 3.61%. HRMS-ESI (−) (m/z): calcd for
[C27H7BF15]−, 627.0401; found, 627.0401.
Compound 15. To a solution of tBu3PAu-CC-ptol (19.2 mg,
0.037 mmol) in CD2Cl2 (0.6 mL) was added B(C6F5)3 (19.1 mg,
0.037 mmol). The solution was stirred for 10 min at room
temperature, and then (Idipp)Au−CC-Me (24.0 mg, 0.037
mmol) was added. The solution was concentrated under reduced
pressure and layered with pentane to afford the desired product as a
colorless solid (45.6 mg, 73%). IR (thin film) νmax = 2965.0 cm−1,
2928, 2873, 1643, 1510, 1460, 1366, 1329, 1273, 1173, 1087, 1075,
Compound 12. B(C6F5)3 (35.2 mg, 0.069 mmol) was added to
tBu-JohnPhosAu-CC-Me (36.7 mg, 0.069 mmol) dissolved in
CH2Cl2 (0.6 mL) and stirred for 30 min. Slow diffusion of pentane
into this solution at −20 °C afforded the product as colorless crystals
(63.0 mg, 88%). IR (thin film) νmax = 2970.6 cm−1, 1643, 1514, 1456,
1392, 1370, 1278, 1174, 1087, 1010, 973, 868, 794, 767, 746, 702, 679.
1H NMR (600 MHz, CD2Cl2, 298 K): δ [ppm] = 7.86 (t, J = 7.4 Hz,
1H), 7.57−7.50 (m, 2H), 7.40−7.36 (m, 1H), 7.33−7.29 (m, 2H),
7.22−7.18 (m, 1H), 7.05 (d, J = 7.4 Hz, 2H), 2.02 (s, 3H), 1.28 (d, J =
16.1 Hz, 18H). 19F NMR (470 MHz, CD2Cl2, 298 K): δ [ppm] =
−131.4 (d, JFF = 22.0 Hz, 6F, o-C6F5), −161.5 (t, JFF = 20.0 Hz, 3F, p-
C6F5), −166.2 (m, 6F, p-C6F5). 31P NMR (243 MHz, CD2Cl2, 298 K):
δ [ppm] = 63.9 (s). 11B NMR (96 MHz, CD2Cl2, 298 K): δ [ppm] =
−19.8 (s). 13C NMR {1H} (150 MHz, CD2Cl2, 298 K): δ [ppm] =
1
804 759, 744. H NMR (500 MHz, CD2Cl2, 298 K): δ [ppm] = 7.54
(t, J = 7.7 Hz, 2H), 7.33 (d, J = 7.7 Hz, 4H), 7.25 (s, 2H), 7.19 (d, J =
7.7 Hz, 2H), 7.00 (d, J = 7.7 Hz, 2H), 2.54 (sept., J = 6.9 Hz, 4H), 2.28
(s, 3H), 2.14 (s, 3H), 1.36 (d, JPH = 14.3 Hz, 27H), 1.30 (d, J = 6.8 Hz,
12H), 1.23 (d, J = 6.8 Hz, 12H). 19F NMR (282 MHz, CD2Cl2, 298
K): δ [ppm] = −132.6 (d, JFF = 24.0 Hz, 6F, o-C6F5), −164.0 (t, JFF
=
20.1 Hz, 3F, p-C6F5), −167.4 (m, 6F, m-C6F5). 11B NMR (96 MHz,
CD2Cl2, 298 K): δ [ppm] = −20.8 (s). 31P NMR (121 MHz, CD2Cl2,
298 K): δ [ppm] = 93.6 (s). 13C NMR {1H} (100 MHz, CD2Cl2, 298
K): δ [ppm] = 183.7 (d, J = 109 Hz), 148.9 (dm, JCF = 241 Hz), 146.3
(s), 138.8 (dm, J = 240 Hz), 137.1 (dm, J = 225 Hz), 136.0 (s), 134.3
(s), 131.5 (s), 131.4 (s), 129.1 (s), 124.9 (s), 124.8 (s), 124.7 (s), 40.0
(d, JCP = 19 Hz), 32.6 (d, JCP = 4 Hz), 29.4 (s), 25.2 (s), 24.1 (s), 21.6
(s), 7.4 (s). Carbon atoms attached to boron could not be observed.
HRMS-ESI (+) (m/z): calcd for [C42H66Au2N2P]+, 1023.4295; found,
1023.4283. HRMS-ESI (−) (m/z): calcd for [C27H7BF15]−, 627.0401;
found, 627.0400.
149.8 (d, JCP = 12.9 Hz), 148.6 (dm, JCF = 240.5 Hz), 142.8 (d, JCP
=
6.3 Hz), 139.5 (dm, JCF = 247.4 Hz), 137.3 (dm, JCF = 245.5 Hz),
134.5 (d, JCP = 3.0 Hz), 134.2 (d, JCP = 7.8 Hz), 131.7 (d, JCP = 2.1
Hz), 130.0 (s), 129.3 (s), 128.4 (s), 127.9 (d, JCP = 7.0 Hz), 124.5 (d,
JCP = 45.4 Hz), 122.0 (brs, C−B), 106.1 (q, J = 60.9 Hz, C−B), 101.3
(brs), 38.7 (d, JCP = 23.9 Hz), 31.0 (d, JCP = 6.6 Hz), 9.33 (s). EA
calcd (%) for C41H30AuBF15P: C 47.06, H 2.89%. Obs. C 46.76, H
2.99%. HRMS-ESI (−) (m/z): calcd for [C21H3BF15]−, 551.0088;
found, 551.0086.
Compound 13. (Idipp)Au-[Ph−CC−B(C6F5)3] (25 mg, 0.021
mmol) in CH2Cl2 (2 mL) was added to PPh3 (5.5 mg, 0.021 mmol) in
CH2Cl2 (2 mL) and stirred overnight going from yellow to colorless.
To the resulting solution was then added hexanes (10 mL), and upon
cooling to −35 °C, X-ray quality white crystals were obtained (28 mg,
Compound 19. To a solution of (Idipp)(4-fluorofluorophenyl)-
gold (17) (34.3 mg, 0.050 mmol) in CH2Cl2 (0.7 mL) was added
B(C6F5)3 (12.9 mg, 0.025 mmol) and stirred for 7 h at room
temperature. The solvent was removed under reduced pressure,
pentane (1 mL) added, and the pentane removed under reduced
vacuum to afford the desired compound 19 as a colorless solid (44.9
mg, 95%). IR (thin film) νmax = 2966.2 cm−1, 2873, 1642, 1590, 1573,
1511, 1458, 1419, 1386, 1365, 1329, 1272, 1220, 1183, 1160, 1082,
1
0.019 mmol, 90% yield). H NMR (400 MHz, CD2Cl2, 298 K): δ
[ppm] = 7.66−7.58 (m, 2H, Ar), 7.53−7.46 (m, 2H, Ar), 7.43−7.28
(m, 13H, Ar), 7.20−7.09 (m, 2H, Ar), 7.05−6.96 (m, 4H, Ar), 2.56
3
3
(sept., 4H,CH-iPr, JHH = 6.6 Hz), 1.26 (d, 12H, −CH3, JHH = 6.6
1
Hz), 1.19 (d, 12H, −CH3, JHH = 6.6 Hz). 11B NMR (128 MHz,
3
1018, 976, 880, 804, 756. H NMR (600 MHz, CD2Cl2, 298 K): 7.49
CD2Cl2, 298 K): δ [ppm] = −20.87 (s). 19F NMR (376 MHz, CD2Cl2,
(t, J = 7.7 Hz, 4H), 7.24 (m, 2H), 7.20 (d, J = 7.8 Hz, 8H), 7.16 (s,
4H), 6.72 (m, 2H), 6.56 (m, 2H), 6.41 (m, 2H), 2.31 (sept., J = 6.8
Hz, 8H), 1.10 (d, J = 6.8 Hz, 24H), 0.85 (d, J = 6.8 Hz, 24H). 19F
NMR (470 MHz, CD2Cl2, 298 K): −104.8 (s, 1F), −122.4 (s, 1F),
−130.5 (d, J = 21.1 Hz, o-C6F5, 6F), −164.6 (t, J = 20.2 Hz, p-C6F5,
4F), −167.4 (m, m-C6F5, 6F). 13C NMR {1H} (150 MHz, CD2Cl2,
298 K): 184.6 (s), 167.3 (d, JCF = 255 Hz), 160.9 (d, JCF = 239 Hz),
149.3 (d, JCF = 8.2 Hz), 148.4 (dm, J = 242 Hz), 146.0 (s), 138.6 (dm,
3
298 K): δ [ppm] = −132.67 (d, 2F, o-C6F5, JFF = 23.9 Hz), −163.92
3
3
(t, 1F, p-C6F5, JFF = 20.3 Hz), −167.38 (t, 2F, m-C6F5, JFF = 21.7
Hz). 31P{1H} NMR (162 MHz, CD2Cl2, 298 K): δ [ppm] = 39.91 (s,
PPh3). 13C{1H} NMR (101 MHz, CD2Cl2, 298 K, partial): δ [ppm] =
189.32 (s, carbene), 146.25 (s, Ar), 134.05 (d, Ar, JPC = 13.8 Hz),
133.50 (s, Ar), 132.62 (d, Ar, JPC = 2.6 Hz), 131.66 (s, Ar), 131.50 (s,
Ar), 129.80 (d, Ar, JPC = 11.7 Hz), 128.17 (s, Ar), 128.12 (s, Ar),
G
dx.doi.org/10.1021/om5006885 | Organometallics XXXX, XXX, XXX−XXX