YANG
5 of 6
(s,12H, o‐CH3), 2.36 (s, 6H, p‐CH3). 13C NMR (CDCl3,
100 MHz, δ, ppm): 150.6 (Ccarbene), 139.2, 138.6, 136.1,
134.9, 129.2, 128.2, 124.3, 122.0, 121.5, 121.2, 109.8, 21.1
(p‐CH3), 19.0 (o‐CH3). IR (KBr, cm−1): 3290, 2918, 1626,
1485, 1471, 1412, 1376, 1354, 1245, 1230, 1092, 953, 858.
Calcd for [(IMes)PdCl2(indazole)] (C28H30Cl2N4Pd) (%):
C, 56.06; H, 5.04; N, 9.34. Found (%): C, 56.22; H, 4.93;
N, 9.45.
4.2.6 | [(SIMes)PdCl2(indazole)] (2b)
The procedure yielded 108 mg (90%) of pure 2b as a yellow
powder. 1H NMR (CDCl3, 400 MHz, δ, ppm): 11.52 (s, 1H,
NH), 8.40 (s, 1H), 7.57–7.55 (m, 1H), 7.33–7.30 (m, 1H),
7.26–7.24 (m, 1H), 7.08–7.04 (m, 1H), 7.01 (br, 4H), 4.05
(s, 4H, NCH2CH2N), 2.61 (s, 12H, o‐CH3), 2.31 (s, 6H,
p‐CH3). 13C NMR (CDCl3, 100 MHz, δ, ppm): 182.5
(Ccarbene), 138.4, 136.9, 134.7, 134.4, 129.7, 129.5, 128.1,
122.0, 121.4, 121.2, 109.7, 51.1 (NCH2CH2N), 21.0
(p‐CH3), 19.2 (o‐CH3). IR (KBr, cm−1): 3313, 2920, 1628,
1493, 1456, 1308, 1272, 1244, 955, 843. Calcd for
[(SIMes)PdCl2(indazole)] (C28H32Cl2N4Pd) (%): C, 55.87;
H, 5.36; N, 9.31. Found (%): C, 56.03; H, 5.61; N, 9.22.
4.2.3
| [(IPr)PdCl2(pyrazole)] (1c)
The procedure yielded 114 mg (90%) of pure 1c as a yellow
1
powder. H NMR (CD2Cl2–DMSO‐d6 (3:1 v/v), 400 MHz,
δ, ppm): 12.01 (s, 1H, NH), 7.75–7.73 (m, 1H), 7.49–7.31
(m, 9H), 6.15–6.13 (m, 1H), 3.09 (sept, J = 6.4 Hz, 4H,
CH(CH3)2), 1.38 (d, J = 6.0 Hz, 12H, CH(CH3)2), 1.09
(d, J = 6.0 Hz, 12H, CH(CH3)2). 13C NMR (CD2Cl2–
DMSO‐d6 (3:1 v/v), 100 MHz, δ, ppm): 152.4 (Ccarbene),
146.2, 138.0, 134.7, 129.4, 129.4, 125.4, 123.2, 104.5, 27.9
(CH(CH3)2), 25.5 (CH(CH3)2), 22.4 (CH(CH3)2). IR (KBr,
cm−1): 3290, 3132, 2957, 2917, 1606, 1486, 1410, 1355,
1229, 1165, 1130, 1061, 1047, 856. Calcd for [(IPr)
PdCl2(pyrazole)] (C30H40Cl2N4Pd) (%): C, 56.83; H, 6.36;
N, 8.84. Found (%): C, 57.04; H, 6.07; N, 8.62.
4.2.7
| [(SIPr)PdCl2(pyrazole)] (2c)
The procedure yielded 115 mg (90%) of pure product 2c as a
yellow powder. 1H NMR (CDCl3, 400 MHz, δ, ppm): 11.56
(s, 1H, NH), 7.85(s, 1H), 7.44–7.2740 (m, 2H), 7.31–7.27
(m, 5H), 6.12(s, 1H), 4.07 (s, 4H, NCH2CH2N), 3.57 (sept,
J = 6.8 Hz, 4H, CH(CH3)2), 1.54 (d, J = 6.8 Hz, 12H,
CH(CH3)2), 1.28 (d, J = 6.8 Hz, 12H, CH(CH3)2). 13C
NMR (CDCl3, 100 MHz, δ, ppm): 185.0 (Ccarbene), 147.4,
138.7, 135.2, 129.3, 127.9, 124.3, 105.4, 53.7 (NCH2CH2N),
28.6 (CH(CH3)2), 26.7 (CH(CH3)2), 24.1 (CH(CH3)2). IR
(KBr, cm−1): 3280, 2966, 1637, 1478, 1455, 1384, 1361,
1267, 1130, 1054, 1017, 801. Calcd for [(SIPr)
PdCl2(pyrazole)] (C30H42Cl2N4Pd) (%): C, 56.65; H, 6.66;
N, 8.81. Found (%): C, 56.45; H, 6.33; N, 8.56.
4.2.4
| [(IPr)PdCl2(indazole)] (1d)
The procedure yielded 120 mg (88%) of pure 1d as a yellow
powder. 1H NMR (CDCl3, 400 MHz, δ, ppm): 11.59
(s, 1H, NH), 8.45 (s, 1H), 7.59–7.57 (m, 1H), 7.53–7.50
(m, 2H), 7.38–7.36 (m, 4H), 7.33–7.31 (m, 1H), 7.28–7.26
(m, 1H), 7.19 (br, 2H), 7.09–7.05 (m, 1H), 3.19 (sept,
J = 6.8 Hz, 4H, CH(CH3)2), 1.51 (d, J = 6.8 Hz, 12H,
CH(CH3)2), 1.16 (d, J = 6.8 Hz, 12H, CH(CH3)2). 13C
NMR (CDCl3, 100 MHz, δ, ppm): 153.2 (Ccarbene), 146.6,
138.6, 134.8, 134.5, 130.2, 128.1, 125.2, 124.0, 122.1,
121.4, 121.2, 109.8, 28.7 (CH(CH3)2), 26.2 (CH(CH3)2),
23.1 (CH(CH3)2). IR (KBr, cm−1): 3290, 3118, 2917, 2866,
1627, 1577, 1483, 1470, 1432, 1383, 1362, 1232, 1087,
998, 911. Calcd for [(IPr)PdCl2(indazole)] (C34H42Cl2N4Pd)
(%): C, 59.70; H, 6.19; N, 8.19. Found (%): C, 59.45; H,
5.99; N, 8.26.
4.2.8
| [(SIPr)PdCl2(indazole)] (2d)
The procedure yielded 110 mg (80%) of pure 2d as a yellow
powder. 1H NMR (CDCl3, 400 MHz, δ, ppm): 11.56 (s, 1H,
NH), 8.42 (s, 1H), 7.58–7.56 (s, 1H), 7.45–7.42 (m, 2H),
7.33–7.25 (m, 6H), 7.08–7.05 (m, 1H), 4.12 (s, 4H,
NCH2CH2N), 3.62 (sept, J = 6.8 Hz, 4H, CH(CH3)2), 1.58
(d, J = 6.4 Hz, 12H, CH(CH3)2), 1.31 (d, J = 6.8 Hz, 12H,
CH(CH3)2). 13C NMR (CDCl3, 100 MHz, δ, ppm): 184.6
(Ccarbene), 147.5, 138.6, 135.1, 134.4, 129.4, 128.1, 124.4,
122.1, 121.4, 121.2, 109.9, 53.8 (NCH2CH2N), 28.7
(CH(CH3)2), 26.7 (CH(CH3)2), 24.1 (CH(CH3)2). IR (KBr,
cm−1): 3341, 2960, 2866, 1627, 1510, 1480, 1452, 1383,
1359, 1300, 1270, 1241, 1094, 1053, 962. Calcd for [(SIPr)
PdCl2(indazole)] (C34H44Cl2N4Pd) (%): C, 59.52; H, 6.46;
N, 8.17. Found (%): C, 59.34; H, 6.77; N, 8.36.
4.2.5
| [(SIMes)PdCl2(pyrazole)] (2a)
The procedure yielded 93 mg (85%) of pure 2a as a yellow
1
powder. H NMR (CD2Cl2–DMSO‐d6 (3:1 v/v), 400 MHz,
δ, ppm): 11.40 (s, 1H, NH), 7.19 (s, 1H), 6.93 (s, 1H), 6.44
(s, 4H), 5.61 (s, 1H), 4.93 (s, 4H), 1.98 (s, 6H, p‐CH3),
1.77 (s, 12H, o‐CH3). 13C NMR (CD2Cl2–DMSO‐d6
(3:1 v/v), 100 MHz, δ, ppm): 181.8 (Ccarbene), 137.8, 137.4,
136.5, 134.5, 129.1, 128.6, 104.5, 50.5, 20.1 (p‐CH3), 18.4
(o‐CH3). IR (KBr, cm−1): 3347, 2922, 1628, 1491, 1455,
1436, 1375, 1310, 1268, 1246, 1025, 949, 842. Calcd for
[(SIMes)PdCl2(pyrazole)] (C24H30Cl2N4Pd) (%): C, 52.23;
H, 5.48; N, 10.15. Found (%): C, 52.41; H, 5.66; N, 10.33.
4.3 | General Procedure for [(NHC)PdCl2(azole)]‐
Catalyzed Suzuki–Miyaura Reaction
A sealable reaction tube was charged with aryl chloride
(0.50 mmol), arylboronic acid (0.60 mmol), [(NHC)
PdCl2(azole)] (0.0005 mmol), NaOH (1.0 mmol) and EtOH
(2.0 ml). The mixture was stirred at room temperature for
6 h. The filtrate was then concentrated and the residue was