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A.O. Biying et al. / Journal of Organometallic Chemistry xxx (2013) 1e5
Table 2
Nano-Pd0/MWCNTs-catalyzed carbonylation of carboranyl ammonium saltsa,b
.
R0
R
H
Me
OMe
Pyridine
H
Me
85
91
74
88
68
77
57
63
a
Reaction conditions: 1.0 mmol of iodobenzene, 1.1 mmol of aniline, 4.0 equiv. of base, 1 mol% Pd catalyst loading in 7 mL anhydrous toluene, PCO ¼ 150 psi,
Temperature ¼ 130 ꢀC, time ¼ 5 h.
b
Isolated yield (%).
resulting crude products were purified with flash column chro-
matography (SiO2, eluted with solvent mixture of hexane and ethyl
acetate in a ratio of 5:1e20:1) to obtain the corresponding amide
products; the reaction scheme and yields are summarized in
Table 2. All products were analyzed by 1H and 13CNMR spectra, FT-
IR, and mass spectra (MS).
1-(CH2NHC(¼O)Ar)-1,2-C2B10H11 (Ar ¼ 2-C5NH4). Yield 57%. MS
(ESI) for C9H18B10N2O: m/z ¼ 323.14 [Mþ2Na]þ, 173.07 [M-
COC5H4N þ H]þ. 1H NMR (CDCl3, ppm),
¼ 8.53e7.44 (m, 4H, C5H4),
d
7.20 (s,1H, NH), 4.08 (d, 2H, CH2eN), 3.89 (s,1H, HCcage), 2.2.81e1.18
(m, br, 10H, B10H10). 13C NMR (CDCl3, ppm),
d
¼ 166.4 (CO),
149.18, 148.20, 136.55, 125.06, 124.11 (C5H4N), 79.46 and 66.20
(Ccage), 47.47 (eCH2eN). 11B NMR (CDCl3, ppm),
1-(CH2NHC(¼O)Ar)-1,2-C2B10H11 (Ar ¼ C6H5). Yield 85%. MS (ESI)
for C10H19B10NO: m/z ¼ 300.24 [M þ Na]þ, 278.25 [M þ H]þ. 1H NMR
d
¼ ꢁ2.92 (1B,
1
1JBH
¼
155 Hz), ꢁ5.53 (1B, JBH
¼
139 Hz), ꢁ9.04 (2B,
(CDCl3, ppm),
d
¼ 7.69e7.32 (m, 5H, C6H5), 6.60 (s, 1H, NH), 4.06 (d,
1JBH ¼ 148 Hz), ꢁ11.72 (2B,1JBH ¼ 133 Hz), ꢁ13.21 (4B,1JBH ¼ 160 Hz).
IR (KBr pellet, cmꢁ1), 3331 (m, s), 3050 (m, s), 2952 (w, s), 2583 (vs,
s),1669 (s, m),1521 (s, m),1309 (m, s),1236 (w, s),1173 (w, s),1121 (w,
s),1093 (w, s),1020 (w, s), 908 (w, s), 836 (w, s), 725 (m, s), 683 (m, s).
1-Me-2-(CH2NH3Cl)-1,2-C2B10H10. The compound was synthe-
sized according to literature in 69% yield [26]. MS (ESI) for
C4H18B10NCl: m/z ¼ 188.25 [M ꢁ Cl]þ. 1H NMR (DMSO-d6, ppm),
2H, CH2eN), 3.99 (s, 1H, HCcage), 1.18e2.66 (m, br, 10H, B10H10). 13
C
NMR (CDCl3, ppm),
(C6H5), 74.20 and 60.61 (Ccage), 45.00 (eCH2eN). 11B NMR (CDCl3,
d
¼ 168.06 (CO), 132.64, 132.59, 128.96, 127.02
ppm),
d
¼ ꢁ1.61 (1B, 1JBH ¼ 148 Hz), ꢁ5.11 (1B, 1JBH ¼ 153 Hz), ꢁ9.82
1
1
(2B, JBH ¼ 154 Hz), ꢁ11.82 (2B, JBH ¼ 148 Hz), ꢁ12.72 (4B,
1JBH ¼ 151 Hz). IR (KBr pellet, cmꢁ1), 3307 (vs, s), 3048 (vs, s), 2626
(m, s), 2575 (vs, s), 1792 (m, m), 1645 (vs, s), 1555 (s, s), 1540 (s, s),
1507 (m, s),1469 (m, s),1311 (m, s),1128 (w, s),1090 (w, s),1018 (w, s),
927 (w, s), 832 (w, s), 780 (w, s), 724 (m, s), 693 (m, s).
d
¼ 3.85 (s, 2H, CH2eN), 2.49 (s, 3H, CcageeCH3) 1.51e2.67 (m, br,10H,
B
10H10). 13C NMR (DMSO-d6, ppm),
d
¼ 77.04 and 74.0164 (Ccage),
40.91 (eCH2eN), 22.38 (CcageeCH3). 11B NMR (DMSO-d6, ppm),
1-(CH2NHC(¼O)Ar)-1,2-C2B10H11 (Ar ¼ 4-Me-C6H5). Yield 74%.
d
¼ ꢁ4.05 (1B, 1JBH ¼ 108 Hz), ꢁ6.33 (1B, 1JBH ¼ 156 Hz), ꢁ10.71 (8B,
MS (ESI) for C11H21B10NO: m/z ¼ 314.25 [M þ Na]þ. 1H NMR (CDCl3,
1JBH ¼ 122 Hz). IR (KBr pellet, cmꢁ1), 3204 (s, br), 2997 (vs, br), 2889
(vs, br), 2588 (vs, s), 2017 (m, s), 1559 (s, br), 1193 (m, s), 1124 (m, s),
1030 (m, s), 1002 (m, s), 730 (s, s), 682 (m, s), 641 (m, s).
ppm),
d
¼ 7.58e7.11 (m, 4H, C6H4), 6.67 (s,1H, NH), 4.02 (d, 2H, CH2-
N), 3.96 (s, 1H, HCcage), 2.31 (s, 3H, CH3), 2.50e1.57 (m, br, 10H,
10H10). 13C NMR (CDCl3, ppm),
¼ 168.08 (CO), 143.30, 129.76,
1-Me-2-(CH2NHC(¼O)Ar)-1,2-C2B10H10 (ArC6H5). Yield 91%. MS
B
d
(ESI) for C11H21B10NO: m/z ¼ 314.25 [M þ Na]þ.1H NMR (CDCl3, ppm),
129.59, 127.06 (C6H4), 75.08 and 60.56 (Ccage), 44.96 (eCH2eN),
d
¼ 7.70e7.32 (m, 5H, C6H5), 6.59 (s, 1H, NH), 4.15 (d, 2H, CH2eN),
21.55 (CH3). 11B NMR (CDCl3, ppm),
d
¼ ꢁ1.60 (1B, 1JBH ¼ 145 Hz),
3.10e1.30 (m, br,10H, B10H10). 2.14 (s, 3H, CH3).13C NMR (CDCl3, ppm),
1
1
ꢁ5.07 (1B, JBH ¼ 147 Hz), -9.77 (2B, JBH ¼ 157 Hz), -11.71 (2B,
1
1JBH ¼ 139 Hz), -12.64 (4B, JBH ¼ 154 Hz). IR (KBr pellet, cmꢁ1),
d
¼ 166.95 (CO),133.16,132.38,128.83, 126.87 (C6H5), 77.84 and 76.10
(Ccage), 41.84 (eCH2eN), 23.50 (CH3).11B NMR (CDCl3, ppm),
d
¼ ꢁ3.48
3346 (vs, s), 3065 (m, s), 3040 (m, s), 2918 (w, s), 2849 (w, s), 2580
(vs, s), 1699 (m, s), 1635 (vs, s), 1541 (vs, s), 1504 (s, s), 1419 (m, s),
1363 (w, s), 1303 (s, s),1193 (m, s), 1119 (m, s),1017 (m, s), 835 (m, s),
751 (s, s), 725 (m, s), 664 (m, s), 629 (m, s).
1
1
1
(1B, JBH ¼ 152 Hz), ꢁ5.78 (1B, JBH ¼ 150 Hz), ꢁ9.77 (5B, JBH
¼
136 Hz), ꢁ10.52 (3B, 1JBH ¼ 114 Hz). IR (KBr pellet, cmꢁ1), 3245 (s, br),
3064(s,br), 2866(m, br), 2590(vs,br),1962(w, s),1785(vs,s),1722(vs,
s),1646 (s, s), 1599 (m, s),1541 (s, s),1451 (s, s), 1424 (m, s), 1314 (s, s),
1277(m, s),1213(vs,s),1173 (s,s),1075(m, s),1017 (s,s),1009 (s,s), 993
(s, s), 940 (m, s), 798 (w, s), 777 (w, s), 702 (vs, s), 615 (m, s).
1-(CH2NHC(¼O)Ar)-1,2-C2B10H11 (Ar ¼ 4-MeOeC6H5). Yield 68%.
MS (ESI) for C11H21B10NO2: m/z ¼ 330.35 [M þ Na]þ. 1H NMR (CDCl3,
ppm),
d
¼ 7.66e6.86 (m, 4H, C6H4), 6.62 (s,1H, NH), 4.02 (d, 2H, CH2-
1-Me-2-(CH2NHC(¼O)Ar)-1,2-C2B10H10 (Ar ¼ 4-Me-C6H5). Yield
N), 3.97 (s, 1H, HCcage), 3.81 (s, 3H, OCH3), 2.28-1.36 (m, br, 10H,
10H10). 13C NMR (CDCl3, ppm),
¼ 167.58 (CO), 163.04, 128.99,
88%. MS (ESI) for C12H23B10NO: m/z ¼ 328.27 [M þ Na]þ. 1H NMR
B
d
(CDCl3, ppm),
d
¼ 7.97e7.19 (m, 4H, C6H4), 6.48 (s, 1H, NH), 4.14 (d,
124.75, 114.14 (C6H4), 75.19 and 60.54 (Ccage), 55.53 (OCH3), 44.97 (e
2H, CH2eN), 2.64e1.57 (m, br, 10H, B10H10), 2.39 (s, 3H, CH3), 2.15 (s,
3H, CcageeCH3). 13C NMR (CDCl3, ppm),
¼ 166.78 (CO), 143.04,
130.64, 129.57, 126.98 (C6H4), 77.94 and 76.14 (Ccage), 41.78 (eCH2e
N), 23.51 (CcageeCH3), 21.53 (CH3). 11B NMR (CDCl3, ppm),
CH2eN). 11B NMR (CDCl3, ppm),
d
¼ ꢁ1.64 (1B, 1JBH ¼ 145 Hz), ꢁ5.11
d
1
1
(1B, JBH ¼ 153 Hz), ꢁ9.80 (2B, JBH ¼ 156 Hz), ꢁ11.69 (2B,
1JBH ¼ 128 Hz), ꢁ12.70 (4B,1JBH ¼ 145 Hz). IR (KBr pellet, cmꢁ1), 3337
(s, s), 3059 (m, s), 3037 (m, s), 2963 (m, s), 2839 (m, s), 2579 (vs, s),
2050 (w, br), 1844 (w, s), 1669 (w, s), 1769 (w, s), 1699 (m, s), 1634 (s,
s), 1606 (s, s), 1541 (s, s), 1507 (s, s), 1457 (s, s), 1419 (s, s), 1319 (s, s),
1302 (s, s), 1264 (s, s), 1180 (s, s),1117 (m, s), 1020 (s, s), 843 (s, s), 768
(s, s), 722 (m, s), 631 (m, s), 610 (m, s).
d
¼ ꢁ3.53
1
1
(1B, JBH ¼ 150 Hz), ꢁ5.80 (1B, JBH ¼ 149 Hz), ꢁ9.80 (5B,
1JBH ¼ 135 Hz), ꢁ10.56 (3B, 1JBH ¼ 116 Hz). IR (KBr pellet, cmꢁ1), 3256
(vs, br, s), 3061 (m, s), 2947 (m, s), 2923 (m, s), 2864 (w, s), 2588 (vs,
s),1921 (w, s),1773 (m, s), 1641 (vs, s),1555 (s, s),1507 (s, s),1448 (m,
j.jorganchem.2013.05.014