E.A. Valishina et al. / Journal of Molecular Catalysis A: Chemical 395 (2014) 162–171
169
ı(C–H from Ar). 1H (CDCl3, ı): 9.47 (s, 1H) and 8.42 (s, 1H,
C
carbene–(NH)NH), 8.15–7.28 and 7.24–6.95 (m, 14H, aryls), 2.49 (s)
1
and 2.45 (s, 12H, Me). 13C{ H} NMR (CDCl3, ı): 180.6 (Ccarbene–NH),
154.8 (C N), 142.9–120.1 (aryls), 19.5, 18.7, and 18.6 (Me).
(16).
Anal.
Calcd
for
C31
H28N4Cl4O2Pd: C, 50.53; H, 3.83; N, 7.60. Found: C, 50.84;
H, 3.78; N, 7.38. ESI+-MS, m/z: 701 [M − Cl]+. IR (KBr, selected
bands, cm−1): 2968–2922 m ꢀ(C–H), 2198 s ꢀ(C N), 1535 s
ꢀ(N C + N–Ccarbene), 838 m ı(C–H from Ar). 1H NMR (CDCl3, ı):
9.75 (s, 1H) and 9.30 (s, 1H, Ccarbene–(NH)NH), 7.50–7.27 and
7.15–6.89 (m, 14H, aryls), 3.91 (s, 3H) and 3.84 (s, 3H, OMe),
(20). Anal. Calcd for C29H22N4Cl4Pd: C,
51.62; H, 3.29; N, 8.30. Found: C, 51.82; H, 3.32; N, 8.30. ESI+-MS,
m/z: 638 [M − Cl]+. IR (KBr, selected bands, cm−1): 2988–2836 m
ꢀ(C–H), 2201 s ꢀ(C N), 1595 s ꢀ(N C), 1533 s ꢀ(N–Ccarbene), 731 m
ı(C–H from Ar). 1H (CDCl3, ı): 9.57 (s, 1H) and 8.40 (s, 1H,
1
2.79 (s, 3H) and 2.20 (s, 3H, Me). 13C{ H} NMR (CDCl3, ı): 178.8
C
carbene–(NH)NH), 8.15–7.38 (m) and 7.15–7.00 (m, 14H, aryls), 2.46
(Ccarbene–NH), 162.4 (C–O), 158.2 (C N), 130.9–127.5 (aryls), 55.7
(OMe), 20.7 and 19.3 (Me).
1
and 2.23 (s, 6H, Me). 13C{ H} NMR (CDCl3, ı): 181.3 (Ccarbene–NH),
154.2 (C N), 142.3–122.8 (aryls), 120.1 (C N), 22.9 and 18.9 (Me).
(21).
Anal.
Calcd
for
C
21H30N4Cl2OPd: C, 47.27; H, 5.69; N, 10.53. Found: C, 46.95;
(17). Anal. Calcd for C27H32N4Cl2Pd:
C, 54.97; H, 5.47 N, 9.49. Found: C, 54.44; H, 5.48; N, 9.69%.
ESI+-MS, m/z: 553 [M − Cl]+, 517 [M − 2Cl −H]+. IR (KBr, selected
bands, cm−1): 2933–2856 m ꢀ(C–H), 2229 s ꢀ(C N), 1575 s
ꢀ(N C + N–Ccarbene), 732 m ı(C–H from Ar). 1H NMR (C DCl3, ı):
10.02 (s, 1H, Ccarbene–NH), 8.15–7.41 (m, 9H, Ccarbene–NH, aryls),
4.45 (s, br, 1H, CH), 4.46 (s, br, 1H, CH), 1.95–1.78 (m, 20H, CH2).
H, 5.77; N, 10.54%. ESI+-MS, m/z: 497 [M − Cl]+. IR (KBr, selected
bands, cm−1): 2932–2856 m ꢀ(C–H), 2228 s ꢀ(C N), 1619 s ꢀ(N C),
1584 s ꢀ(N–Ccarbene), 753 m ı(C–H from Ar). 1H NMR (CDCl3, ı):
9.64 (s, 1H) and 8.90 (s, 1H, Ccarbene–(NH)NH), 8.71 (s, 1H, OH),
7.40–7.31 (m) and 7.05–6.59 (m, 4H, aryls), 4.69 (s, br) and 4.01
(s, br, 2H, CH), 1.82–1.37 (m, 20H, CH2). 13C{ H} NMR (CDCl3,
1
1
13C{ H} (CDCl3, ı): 175.0 (Ccarbene–NH), 155.5 (C N), 132.9–120.4
ı): 172.6 (Ccarbene–NH), 166.7 (C N), 153.4 (C–OH), 133.6–132.7
(aryls), 117.2 (C N), 58.7 and 55.5 (CH), 33.8–22.7 (CH2).
(aryls), 68.4 (CH), 68.6 (CH), 35.4–22.3 (CH2).
t-Bu
H
N
N
Cl
C
N
H
Pd
Cl
C
(22).
Anal.
Calcd
for
N
C17H26N4Cl2OPd: C, 42.56; H, 5.46; N, 11.68. Found: C, 42.64;
H, 5.51; N, 11.50%. ESI+-MS, m/z: 407 [M − 2Cl − H]+. IR (KBr,
selected bands, cm−1): 2981–2935 m ꢀ(C–H), 2228 s ꢀ(C N), 1621
s ꢀ(N C), 1570 s ꢀ(N–Ccarbene), 749 m ı(C–H from Ar). 1H NMR
(CDCl3, ı): 9.63 (s, 1H), 9.04 (s, 1H, Ccarbene–(NH)NH), 8.74 (s, 1H,
OH), 7.39–6.98 (m, 4H, aryls), 3.49 (s, 1H, CH), 1.80–1.60 (m, 18H,
t-Bu
(18). Anal. Calcd for C23H28N4Cl2Pd: C,
51.36; H, 5.26; N, 10.42. Found: C, 51.67; H, 5.27; N, 10.53%. ESI+-
MS, m/z: 539 [M + H]+. IR (KBr, selected bands, cm−1): 2982–2931 m
ꢀ(C–H), 2228 s ꢀ(C N), 1609 s ꢀ(N C), 1569 s ꢀ(N–Ccarbene),
731 m ı(C–H from Ar). 1H NMR (CDCl3, ı): 9.86 (s, 1H) and 9.11
(s, 1H, Cca1rbene–(NH)NH), 8.14–7.38 (m, 8H, aryls), 1.80 (s, 18H,
Me). 13C{ H} NMR (CDCl3, ı): 207.1 (Ccarbene–NH), 154.9 (C N),
142.4–120.2 (aryls), 115.8 (C N), 59.2 (CMe3), 30.0 (CMe3).
1
Me). 13C{ H} NMR (CDCl3, ı): 164.8 (Ccarbene–NH and C N), 159.9
(C–OH), 133.6–132.7 (aryls), 117.3 (C N), 55.3 (CMe3), 31.7 and
30.1 (CMe3).
(23).
Anal.
Calcd
for
C25H26N4Cl2OPd: C, 52.15; H, 4.55; N, 9.73. Found: C, 52.15;
H, 4.63; N, 9.78. ESI+-MS, m/z: 541 [M − Cl]+. IR (KBr, selected
bands, cm−1): 2967–2896 m ꢀ(C–H), 2207 s ꢀ(C N), 1620 s
ꢀ(N C), 1568 s ꢀ(N–Ccarbene), 771 m ı(C–H from Ar). 1H NMR
(CDCl3, ı): 9.21 (s, 1H) and 8.82 (s, 1H, Ccarbene–(NH)NH), 8.14
(19). Anal. Calcd for C31H28N4Cl2Pd: C,
58.74; H, 4.45; N, 8.84. Found: C, 58.60; H, 4.65; N, 8.80 ESI+-MS,
m/z: 599 [M − Cl]+. IR (KBr, selected bands, cm−1): 2965–2921 m
ꢀ(C–H), 2199 s ꢀ(C N), 1597 s ꢀ(N C), 1528 s ꢀ(N–Ccarbene), 783 m