(0.022 g, 0.098 mmol) was added to two equivalents of B(C6F5)3
(0.10 g, 0.20 mmol) in 5 mL of dichloromethane. The solution was
subjected to three freeze–pump–thaw cycles and backfilled with
H2 at 77 K (4 atm). The solution was allowed to stir overnight at
room temperature and then pumped to dryness. The solid was
washed with hexane (2 ¥ 2 mL) and again pumped to dryness.
Yield: 112 mg (90%)
NMR (CDCl3) partial: 122.4, 122.8, 126.4, 128.0, 131.4, 136.7,
149.9; 19F NMR (CDCl3): -133.0 (br s, 6F, o-C6F5), -156.4 (t,
3JF–F = 20 Hz, 3F, p-C6F5), -163.1 (t, 3JF–F = 20 Hz, 6F, m-C6F5);
11B NMR (CDCl3): -5.8 (br s); Anal. Calcd. for C27H8BF15N2 (%)
C: 49.42, H: 1.23, N: 4.27; found C: 48.92, H: 1.23, N: 4.08.
9: Yield: 110 mg (91%). 1H NMR (CDCl3): 9.90 (br s, 1H, NH),
7.88 (dd, 3JH–H = 9 Hz, 3JH–H = 7 Hz, 1H, p-CH), 6.88 (d, 3JH–H
=
1H NMR (CD2Cl2): 12.69 (br. s, NH, 1H), 7.69 (s, CH, 2H),
7.55 (s, CH(NO-ring), 2H), 3.48 (q, 1JB–H = 60 Hz, BH, 1H), 2.80
(s, CH3, 6H), 2.72 (s, CH3(NO-ring), 6H); 13C NMR (CD2Cl2)
partial: 19.98, 20.67, 123.88, 124.43, 144.04, 152.40, 155.98,
158.48; 19F NMR (CD2Cl2): -127.80 (s, 2F, o-C6F5), -132.20 (s, 2F,
o-C6F5) -133.73 (s, 2F, o-C6F5), -134.26 (d, 3JF-F = 20 Hz, o-C6F5,
6F) -154.69 (br s, 1F p-C6F5), -159.37 (br. s, 2F p-C6F5), -162.95
(t, 3JF–F = 20 Hz, p-C6F5, 3F) -163.55 (s, 2F, m-C6F5), -164.61 (s,
2F, m-C6F5), -165.25 (s, 2F, m-C6F5), -166.56 (td, 3JF–F = 20 Hz,
4JF–F = 8 Hz, m-C6F5, 6F); 11B NMR (CD2Cl2): 2.85 (br. s), -24.70
7 Hz, 1H), 6.71 (d, JH–H = 10 Hz, 1H), 2.65 (s, 3H, CH3); 13C
3
NMR (CDCl3) partial: 19.9, 112.7, 114.4, 147.0, 147.3, 161.7. 19
F
3
NMR (CDCl3): -134.1 (d, JF–F = 23 Hz, 6F, o-C6F5), -157.8 (t,
3JF–F = 20 Hz, 3F, p-C6F5), -164.0 (tm, 3JF–F = 22 Hz, 6F, m-C6F5);
11B NMR (CDCl3): -1.5 (s); Anal. Calcd. for C24H7BF15NO (%)
C: 46.41, H: 1.14, N: 2.26; found C: 45.97, H: 1.37, N: 2.79.
1
10: Yield: 119 mg (91%). H NMR (CDCl3): 11.10 (br s, 1H,
3
3
NH), 7.48 (dd, JH–H = 9 Hz, JH–H = 7 Hz, 1H, p-CH), 6.58 (d,
3JH–H = 9 Hz, 1H), 6.46 (br s, 1H, NH), 6.38 (d, JH–H = 7 Hz,
3
1H), 2.39 (s, 3H, CH3); 13C NMR (CDCl3) partial: 19.6, 110.4,
1
(d, BH, JB–H = 83 Hz); Anal. Calcd. for C32H16BF15N2O (%) C:
114.4, 142.5, 144.8, 155.2. 19F NMR (CDCl3): -133.5 (dd, 3JF–F
=
4 3
51.92, H: 2.18, N: 3.78; found C: 51.84, H: 2.76, N: 3.33.
23 Hz, JF–F = 8 Hz 6F, o-C6F5), -155.9 (t, JF–F = 21 Hz, 3F, p-
3 4
C6F5), -162.3 (td, JF–F = 21 Hz, JF–F = 8 Hz, 6F, m-C6F5); 11B
NMR (CDCl3): -2.8 (br. s); Anal. Calcd. for C18H8BClF15N2 (%)
C: 44.25, H: 1.65, N: 5.73; found C: 44.19, H: 1.94, N: 5.55.
11: Yield: 73 mg (87%). Crystals for X-ray diffraction were
Synthesis of (C5H3(6-CF3)NH)(2-NH(B(C6F5)3)) (6), (C9-
H6NH)(2-NHB(C6F5)3) (7), (C9H6N)(8-NH2B(C6F5)3) (8), (C5-
H3(6-Me)NH)(2-OB(C6F5)3) (9), (C5H3(6-R)NH)(2-NH(ClB-
(C6F5)2)) (R = Me (10), R = CF3 (11)) (C9H6NH)(2-NH(ClB-(C6-
F5)2)) (12), (C9H6N)(8-NH2ClB(C6F5)2) 13, (C5H3(6-Me)NH)(2-
OClB(C6F5)2) 14, (C5H3(6-Me)NH)(2-NH(HB(C6F5)2)) 15,
(C9H6NH)(2-NH(HB(C6F5)2)) 16, (C9H6N)(8-NHB(C6F5)2) 17,
(C5H3(6-CF3)N)(2-NH(B(C6F5)2) 18). These compounds were
prepared in a similar fashion and thus only one preparation is
detailed. For example: 2-amino-6-CF3-pyridine (32 mg, 0.040
mmol) was added to a solution of B(C6F5)3 (100 mg, 0.039 mmol)
in CH2Cl2 (2 mL), The solution was allowed to stand for 2 h,
then all volatiles were removed and the residue was washed with
pentane (2 ¥ 2 mL). The resulting white solid 6 was dried in vacuo.
6: Yield: 124 mg (95%). Crystals for X-ray diffraction were
grown from the hexane wash layer. 1H NMR (CDCl3): 8.96 (br s,
1H, NH), 7.64 (dd, 3JH–H = 8 Hz, 3JH–H = 7 Hz, 1H, CH), 7.01 (d,
3JH–H = 9 Hz, 1H, CH), 6.87 (d, 3JH–H = 7 Hz, 1H, CH), 6.74 (br s,
1
grown from the hexane wash layer. H NMR (CDCl3): 11.59 (br
s, 1H, NH); 7.79 (t, 3JH–H = 8 Hz, 3JH–H = 7 Hz, 1H, p-CH), 7.07
(br m, 3H), 13C NMR (CDCl3) partial: 109.9, 117.8, 120.6, 121.3,
137.4 (dm, 1JC–F = 255 Hz, CF), 140.6 (dm, 1JC–F = 255 Hz, CF),
140.9, 147.8, (dm, 1JC–F = 244 Hz, CF), 154.9; 19F NMR (CDCl3):
-66.9 (s, 3F, CF3), -133.3 (br d, 3JF–F = 19 Hz, 4F, o-C6F5), -154.7
(br s, 2F, p-C6F5), -161.9 (br s, 4F, m-C6F5); 11B NMR (CDCl3):
0.4 (br s); Anal. Calcd. for C18H9BF15N2 (%) C: 39.85, H: 0.93, N:
5.16; found C: 40.12, H: 0.93, N: 5.00.
12: Yield: 87 mg (96%). Crystals for X-ray diffraction were
1
grown from the hexane wash layer. H NMR (CDCl3): 11.10 (br
s, 1H, NH), 8.03, (d, 3JH–H = 9 Hz, 1H), 7.76 (t, 3JH–H = 8 Hz, 1H),
3
3
7.75 (d, JH–H = 8 Hz, 1H), 7.52 (d, JH–H = 8 Hz, 1H), 7.50 (t,
3JH–H = 8 Hz, 1H), 7.06 (br s, 1H, NH), 6.89 (d, 3JH–H = 9 Hz, 1H),
13C NMR (CDCl3) partial: 116.9, 117.4, 120.8, 125.7, 128.7, 133.0,
141.8, 154.5; 19F NMR (CDCl3): -133.5 (d, 3JF–F = 21 Hz, 6F, o-
1H, NH); 19F NMR (CDCl3): -67.8 (s, 3F, CF3), -133.3 (d, 3JF–F
=
3
3
3
22 Hz, 6F, o-C6F5), -155.3 (t, JF–F = 21 Hz, 3F, p-C6F5), -164.1
C6F5), -155.7 (t, JF–F = 20 Hz, 3F, p-C6F5), -162.2 (td, JF–F =
4
(tm, 3JF–F = 22 Hz, 6F, m-C6F5); 11B NMR (CDCl3): -10.9 (s); 13
C
20 Hz, JF–F = 8 Hz, 6F, m-C6F5); 11B NMR (CDCl3): -3.0 (s);
Anal. Calcd. for C21H8BClF10N2 (%) C: 48.08, H: 1.54, N: 5.34;
found C: 47.84, H: 1.79, N: 5.41.
1
NMR (CDCl3) partial: 108.5, 122.0, 137.4, (dm, JC–F = 255 Hz,
CF), 140.0, 148.1, (dm, 1JC–F = 239 Hz, CF), 154.6. Anal. Calcd.
for C24H5BF18N2 (%) C: 42.76, H: 0.75, N: 4.16; found C: 42.73,
H: 0.95, N: 4.24.
1
13: Yield: 78 mg (86%). H NMR (CDCl3) partial: 8.88 (d,
3JH–H = 5 Hz, 1H), 8.43 (d, JH–H = 8 Hz, 1H), 7.65 (dd, JH–H
=
=
3
3
7: Yield: 119 mg (93%). 1H NMR (CDCl3): 8.91 (br s, 1H, NH),
7 Hz, 3JH–H = 5 Hz, 1H), 7.50 (t, 3JH–H = 8 Hz, 1H), 6.98 (d, 3JH–H
3
3
7.94 (d, JH–H = 10 Hz, 1H), 7.71 (d, JH–H = 8 Hz, 1H), 7.67 (t,
7 Hz, 1H), 6.76 (d, 3JH–H = 7 Hz, 1H); 13C NMR (CDCl3) was not
obtained due to poor solubility; 19F NMR (CDCl3): -134.9 (br s,
6F, o-C6F5), -156.3 (br s, 3F, p-C6F5), -163.1 (br s, 6F, m-C6F5);
11B NMR (CDCl3): 2.7 (br s); Anal. Calcd. for C21H8BClF10N2 (%)
C: 48.08, H: 1.54, N: 5.34; found C: 47.26, H: 1.83, N: 5.17
14: Yield: 80 mg (90%). 1H NMR (CDCl3): 11.96 (br s, 1H, NH),
8.00 (t, 3JH–H = 8, 1H, p-CH), 7.16 (d, 3JH–H = 8 Hz, 1H), 6.96 (d,
3JH–H = 7 Hz, 1H), 2.65 (s, 3H, CH3); 13C NMR (CDCl3) partial:
19.9, 115.4, 116.0, 146.6, 146.8, 161.2;. 19F NMR (CDCl3): -134.0
(dd, 3JF–F = 22 Hz, 4JF–F = 7 Hz, 6F, o-C6F5), -156.8 (t, 3JF–F = 21 Hz,
3F, p-C6F5), -163.8 (td, 3JF–F = 21 Hz, 4JF–F = 8 Hz, 6F, m-C6F5);
11B NMR (CDCl3): 3.4 (s); Anal. Calcd. for C18H7BClF10NO (%)
C: 44.17, H: 1.44, N: 2.86; found C: 44.12, H: 1.31, N: 3.19.
3JH–H = 8 Hz, 1H), 7.45 (t, 3JH–H = 8 Hz, 1H), 7.08 (d, 3JH–H = 8 Hz,
1H), 6.86 (dd, JH–H = 7 Hz, JH–H = 2 Hz, 1H), 6.70 (br s, 1H,
NH); 13C NMR (CDCl3) partial: 116.1, 116.9, 120.4, 125.5, 128.8,
3
4
1
1
133.0, 135.2, 137.3 (dm, JC–F = 260 Hz, CF), 148.1 (dm, JC–F
=
246 Hz, CF), 154.4. 19F NMR (CDCl3): -132.7 (d, 3JF–F = 20 Hz,
3
6F, o-C6F5), -155.8 (t, JF–F = 21 Hz, 3F, p-C6F5), -162.0 (tm,
3JF–F = 20 Hz, 6F, m-C6F5); 11B NMR (CDCl3): -10.7 (s); Anal.
Calcd. for C27H8BF15N2 (%) C: 49.42, H: 1.23, N: 4.27; found C:
48.45, H: 1.18, N: 4.47.
1
3
8: Yield: 111 mg (87%). H NMR (CDCl3): 8.84 (d, JH–H
4 Hz, 1H), 8.39 (br s, 2H, NH2), 8.25 (d, 3JH–H = 8 Hz, 1H), 7.82
(d, 3JH–H = 8 Hz, 1H), 7.67 (d, 3JH–H = 7 Hz, 1H), 7.55 (m, 2H); 13
=
C
This journal is
The Royal Society of Chemistry 2012
Dalton Trans., 2012, 41, 2131–2139 | 2133
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