T. Terashima, S. Inomata, K. Ogata, S. Fukuzawa
CCDC-827678 (for 9), -854140 (for 10a), -854142 (for 10b), -854141 CHCH3), 2.78 (sept, J = 6.8 Hz, 1 H, CHCH3), 2.86 (d, J =
FULL PAPER
(for 10c) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
13.4 Hz, 1 H, allyl), 2.91–3.05 (m, 3 H, CHCH3 and allyl), 3.85 (s,
3 H, NCH3), 3.92 (dd, J = 1.9, 7.4 Hz, 1 H, allyl), 4.88 (m, 1 H,
allyl-CH), 7.28–7.31 (d, J = 7.8 Hz, 4 H), 7.48 (t, J = 7.8 Hz, 1 H),
7.49 (t, J = 7.8 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
22.5, 22.5, 24.1, 24.3, 24.5, 24.6, 25.3, 26.1, 28.7, 29.0, 30.9, 36.7,
48.5, 72.2, 113.7, 123.5, 123.6, 124.3, 130.6, 130.9, 136.7, 144.1
145.4, 149.4, 149.6, 171.8 (C-Pd) ppm. C30H42ClN3Pd (586.53):
calcd. C 61.43, H 7.22, N 7.16; found C 61.07, H 7.27, N 7.11.
Preparation of Triazolium Salt 6c: The triazole 5c (0.71 mmol) and
Me3OBF4 (154 mg, 1.04 mmol) were stirred under nitrogen in dry
dichloromethane (15 mL) for 48 h. The reaction was quenched with
MeOH (1 mL), and the solvent was removed under reduced pres-
sure to give the crude product, which was then washed with diethyl
ether and dried to give the triazolium salt. White solid; 254 mg,
(Crotyl)(TPr)PdCl (10b): White solid; 79 mg, 63% yield; m.p.
167 °C (dec). An analytically pure sample was obtained by
76% yield; m.p. 222–223 °C. 1H NMR (400 MHz, CDCl3): δ = 1.15 recrystallization of 10b from benzene and hexane. 1H NMR
(d, J = 6.8 Hz, 6 H, CH3), 1.22 (d, J = 6.8 Hz, 6 H, CH3), 1.29 (d, (300 MHz, CDCl3): δ = 1.09 (d, J = 6.9 Hz, 3 H, CH3), 1.13 (d, J
J = 6.8 Hz, 6 H, CH3), 1.33 (d, J = 6.8 Hz, 6 H, CH3), 2.30–2.40
= 6.9 Hz, 3 H, CH3), 1.15 (d, J = 6.9 Hz, 3 H, CH3), 1.15 (d, J =
(m, 4 H, CHCH3), 4.26 (s, 3 H, NCH3), 7.39 (d, J = 6.3 Hz, 2 H), 6.9 Hz, 3 H, CH3), 1.25–1.38 (m, 13 H), 1.42 (d, J = 6.2 Hz, 3 H,
7.41 (d, J = 6.3 Hz, 2 H), 7.63 (t, J = 8.1 Hz, 1 H), 7.65 (t, J = crotyl-CH3), 2.60–2.69 (m, 2 H, 2 CHCH3), 2.76–2.98 (m, 3 H,
8.1 Hz, 1 H), 8.55 (s, 1 H, tzH) ppm. 13C NMR (75 MHz, CDCl3):
δ = 22.8, 23.6, 23.8, 24.7, 29.0, 31.7, 38.5, 117.2, 124.1, 124.6, 130.6,
133.0, 133.1, 142.0, 145.0, 148.9 ppm. C27H38BF4N3·0.5H2O: calcd.
C 64.80, H 7.86, N 8.40; found C 65.18, H 7.91, N 8.43.
CHCH3 and allyl), 3.55 (sext, J = 6.2 Hz, 1 H, crotyl-CH), 3.85 (s,
3 H, NCH3), 4.59 (ddd, J = 11.6, 11.6, 6.5 Hz, 1 H, crotyl-CH),
7.27–7.31 (m, 4 H), 7.45–7.51 (m, 2 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 17.0, 22.6, 22.6, 24.1, 24.2, 24.4, 24.5, 25.4, 25.9, 28.7,
28.9, 30.9, 36.7, 43.9, 89.4, 112.6, 123.4, 123.5, 123.6, 124.6, 130.5,
130.8, 136.8, 144.3 145.3, 145.5, 149.4, 172.0 (C-Pd) ppm.
C31H44ClN3Pd (600.56): calcd. C 62.00, H 7.38, N 7.00; found C
62.05, H 7.49, N 6.98.
Synthesis of (Allyl)(1,2,3-triazol-5-ylidene)palladium Complexes (R-
allyl)(tzNHC)PdCl: The following provides a general procedure for
the synthesis of (R-allyl)(tzNHC)PdCl. Under nitrogen, Ag2O
(25 mg, 0.12 mmol) and Me4NCl (24 mg, 0.22 mmol) were added
to a solution of a triazolium salt 6a–6c (70 mg, 0.22 mmol) in ace-
tonitrile/dichloromethane (1:1, 12 mL) and the suspension was
stirred in a Schlenk tube covered with foil at room temperature
for 5 h. [(R-η3-allyl)PdCl]2 (42 mg, 0.11 mmol) was added to the
solution that was then stirred overnight. The solvent was removed
under vacuum, and the residue was extracted with dichloromethane
and filtered through a Celite pad. The filtrate was concentrated,
and then the crude palladium complex was purified by PTLC (silica
gel; 20% EtOAc/hexanes).
(Cinnamyl)(TPr)PdCl (10c): Yellow solid; 94 mg, 68% yield; m.p.
78–80 °C. An analytically pure sample was obtained by recrystalli-
zation of 10c from benzene and hexane. 1H NMR (300 MHz,
CDCl3): δ = 1.11–1.16 (m, 12 H), 1.27–1.41 (m, 12 H), 1.84 (d, J
= 11.6 Hz, 1 H, cinnamyl), 2.81 (br. m, 5 H), 3.85 (s, 3 H, NCH3),
4.42 (d, J = 12.7 Hz, 1 H, cinnamyl), 5.13–5.21 (m, 1 H, cinnamyl),
7.10–7.21 (m, 5 H), 7.29–7.32 (m, 4 H), 7.48–7.52 (m, 2 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 22.5, 22.7, 24.1, 24.4, 25.5, 25.7,
28.8, 30.8, 36.7, 45.3, 89.8, 108.3, 123.5, 124.4, 126.3, 127.2, 128.1,
130.5, 130.9, 136.6, 138.1, 144.2 145.4, 149.3, 170.1 (C-Pd) ppm.
C36H46ClN3Pd (662.63): calcd. C 65.25, H 7.00, N 6.34; found C
65.36, H 7.13, N 6.32.
(Allyl)(TPh)PdCl (8): Off-white solid; 93 mg, 99% yield; m.p. 100–
1
101 °C. H NMR (300 MHz, CDCl3): δ = 1.87 (d, J = 11.7 Hz, 1
H, allyl), 2.90 (d, J = 7.0 Hz, 1 H, allyl), 3.10 (d, J = 14.1 Hz, 1
H, allyl), 4.14 (d, J = 7.0 Hz, 1 H, allyl), 4.17 (s, 3 H, NCH3), 4.95– (TMes)Ir(CO)2Cl (11a): Yellow solid; 38 mg, 90% yield; m.p. 227–
1
5.03 (m, 1 H, allyl-CH), 7.49–7.56 (m, 6 H), 7.95 (d, J = 8.2 Hz, 1
228 °C. H NMR (300 MHz, CDCl3): δ = 2.17 (s, 6 H, CH3), 2.20
H), 8.33 (d, J = 7.0 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ (s, 6 H, CH3), 2.36 (s, 3 H, CH3), 2.38 (s, 3 H, CH3), 3.86 (s, 3 H,
= 37.4, 48.3, 71.1, 113.7, 123.9, 127.7, 128.6, 128.8, 129.5, 129.7,
130.0 139.9, 146.4, 166.6 (C-Pd) ppm. C18H18ClN3Pd (418.21):
calcd. C 51.69, H 4.34, N 10.05; found C 51.39, H 4.21, N 10.01.
NCH3), 7.03 (s, 4 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 18.1,
20.6, 21.3, 21.4, 36.3, 122.5, 128.9, 129.2, 134.6, 135.5, 138.2, 140.5,
140.6, 146.6, 166.5 (C-Ir), 168.9 (CO), 181.0 (CO) ppm. IR
(CH Cl ): ν = 2062, 1976 [ν(CO)] cm–1. C H ClIrN O (603.14):
˜
2
2
23 25
3
2
(Allyl)(TMes)PdCl (9): Pale yellow solid; 224 mg, 99% yield; m.p.
calcd. C 45.80, H 4.18, N 6.97; found C 45.72, H 4.08, N 6.91.
151 °C (dec). An analytically pure sample was obtained by
recrystallization of
9
from CH2Cl2 and hexane. 1H NMR
(TPr)Ir(CO)2Cl (11b): Yellow solid; 61 mg, 61% yield; m.p. 180–
(300 MHz, CDCl3): δ = 1.84 (d, J = 11.7 Hz, 1 H, allyl), 2.15–2.20 181 °C. 1H NMR (300 MHz, CDCl3): δ = 1.11 (d, J = 6.9 Hz, 6
(m, 12 H, 4 CH3), 2.33 (s, 3 H), 2.34 (s, 3 H), 2.88 (d, J = 13.5 Hz, H, CH3), 1.15 (d, J = 6.9 Hz, 6 H, CH3), 1.36 (d, J = 6.7 Hz, 6 H,
1 H, allyl), 3.10 (d, J = 7.6 Hz, 1 H, allyl), 3.84 (s, 3 H, NCH3),
3.90 (dd, J = 7.0, 2.1 Hz, 1 H, allyl), 4.84–4.97 (m, 1 H, allyl-CH),
CH3), 1.39 (d, J = 6.7 Hz, 6 H, CH3), 2.67–2.83 (m, 4 H, 4
CHCH3), 3.87 (s, 3 H, NCH3), 7.34 (d, J = 7.8 Hz, 4 H), 7.49 (t,
6.98 (s, 4 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 17.7, 20.4, J = 7.8 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 22.2, 24.2,
21.1, 21.2, 35.9, 47.5, 71.7, 113.8, 123.8, 128.5, 128.8, 134.7, 136.3,
138.3, 139.6 139.8, 145.0, 169.7 (C-Pd) ppm. C24H30ClN3Pd
(502.37): calcd. C 57.38, H 6.02, N 8.36; found C 57.23, H 6.04, N
8.30.
24.8, 25.9, 29.3, 31.2, 37.1, 122.7, 123.8, 124.0, 131.3, 131.5, 135.6,
145.4, 149.5, 168.1 (C-Ir), 169.1 (CO), 180.7 (CO) ppm. IR
(CH Cl ): ν = 2062, 1976 [ν(CO)] cm–1. C H ClIrN O (687.30):
˜
2
2
29 37
3
2
calcd. C 50.7, H 5.43, N 6.11; found C 50.70, H 5.43, N 6.09.
(Allyl)(TPr)PdCl (10a): White solid; 119 mg, 78% yield; m.p. 170–
171 °C (dec). An analytically pure sample was obtained by
recrystallization of 10a from toluene and hexane. 1H NMR
(400 MHz, CDCl3): δ = 1.06 (d, J = 6.9 Hz, 3 H, CH3), 1.11 (d, J
General Procedure for the Room-Temperature Suzuki–Miyaura Cou-
pling Reactions: Under nitrogen, a 20 mL Schlenk tube containing
a stirring bar was charged with potassium tert-butoxide (62 mg,
0.55 mmol), palladium catalyst (0.005 mmol), arylboronic acid
= 6.9 Hz, 3 H, CH3), 1.16 (d, J = 6.9 Hz, 3 H, CH3), 1.17 (d, J = (64 mg, 0.53 mmol), aryl chloride (0.5 mmol) and dry EtOH
6.9 Hz, 3 H, CH3), 1.30 (d, J = 6.9 Hz, 3 H, CH3), 1.33 (d, J = (1.5 mL). The mixture was stirred at room temperature for 1 h. The
6.9 Hz, 3 H), 1.35 (d, J = 6.9 Hz, 3 H), 1.37 (d, J = 6.9 Hz, 3 H), reaction was quenched with water, and the mixture was extracted
1.74 (d, J = 11.8 Hz, 1 H, allyl), 2.61 (sept, J = 6.8 Hz, 1 H, with EtOAc, dried with MgSO4, and filtered. GC–MS analysis of
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Eur. J. Inorg. Chem. 2012, 1387–1393