A solution of B(C6F5)3 (121.5 mg, 0.237 mmol) in pentane (10 mL) was added to the flask. After stirring overnight, a white insoluble powder was collected via ...
Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is © The Royal Society of Chemistry 2015
Supplementary Data for:
Reactions of Iodine-Nitrene Reagents with Boranes† Shawn Postle and Douglas W. Stephan*
Synthesis of (C6F5)2BN(Ts)(C6F5) 1: A 50 mL Schlenk flask was charged with TsN=IPh (88.6 mg, 0.237 mmol) in pentane (10 mL) to form a white slurry. A solution of B(C6F5)3 (121.5 mg, 0.237 mmol) in pentane (10 mL) was added to the flask. After stirring overnight, a white insoluble powder was collected via filtration. The crude product was dissolved in a small volume of CH2Cl2 (2 mL) and filtered through a plug of celite. The filtrate was collected and stored at – 35 °C to allow for the formation of small clear, colourless crystals. Yield 120 mg (74 %). 1H NMR (400 MHz, C6D6, 25 °C): δ 7.35 (d, 3JH-H = 8 Hz, 2H, CH tol), 6.49 (d, 3JH-H = 8 Hz, 2H, CH tol), 1.75 (s, 3H, tol CH3). 11B{1H} NMR (128 MHz, C6D6, 25 °C): δ 43.6 (br). 19F (376 MHz, C6D6, 25 °C): δ – 128.60 (m, 2F, o-F (C6F5)), – 131.35 (m, 2F, o-F (C6F5)), – 142.19 (m, 2F, o-F N(C6F5)), – 146.68 (t, 3JF-F = 21 Hz, 1F, p-F (C6F5)), – 148.69 (t, 3JF-F = 22 Hz, 1F, p-F N(C6F5)), – 150.02 (t, 3JF-F = 19 Hz, 1F, p-F (C6F5)), – 159.04 (m, 2F, m-F (C6F5)), – 160.27 (m, 2F, m-F N(C6F5)), – 161.06 (m, 2F, m-F (C6F5)). HRMS (EI-TOF) m/z: [M]+ Calcd for C25H7BF15NO2S 681.0085, Found 681.0068.
Synthesis of (C6F5)2BN(Ts)(C6F5) · OPEt3 2: A 4 dram scintillation vial was charged with 1 (53.3 mg, 0.0782 mmol) in toluene (1 mL). To the solution, OPEt3 (10.5 mg, 0.0783 mmol) was added. The solution was left at room temperature overnight to afford large rectangular crystals, suitable for x-ray diffraction. Yield 56.1 mg (88 %). 1H NMR (400 MHz, tol-d8, 25 °C): δ 7.64 (d, 3JH-H = 8 Hz, 2H, tol CH), 6.66 (d, 3JH-H = 8 Hz, 2H, tol CH), 1.88 (m, 6H, CH2 Et CH2), 1.84 (s, 3H, tol CH3), 0.68 (dt, 3JP-H = 18 Hz, 3JH-H = 8 Hz, 9H, Et CH3). 11B{1H} NMR (128 MHz, tol-d8, 25 °C): δ 1.41 (s). 19F (376 MHz, tol-d8, 25 °C): δ – 133.44 (br, 4F, o-F B(C6F5)), – 137.99 (s, 2F, o-F N(C6F5)), – 154.59 (s, 1F, p-F N(C6F5)), – 156.70 (br, 2F, p-F B(C6F5)), – 163.86 (br, 4F, m-F B(C6F5)), – 164.10 (s, 2F, m-F N(C6F5)). 31P{1H} NMR (162MHz, tol-d8, 25 °C): δ 78.50 (s).
Synthesis of (C6F5)2BN(Ph)Ts 3: A 50 mL Schlenk flask was charged with TsN=IPh (17.4 mg, 0.0466 mmol) in pentane (10 mL). To the flask, a solution of PhB(C6F5)2 (19.7 mg, 0.0467 mmol) in pentane (10 mL) was added. The reaction mixture was allowed to stir overnight. A white solid was collected via filtration. The solid was redissolved in CH2Cl2 and cooled to – 35 °C to afford clear colourless crystals. Yield 20.9 mg (76 %). 1H NMR (400 MHz, tol-d8, 25 °C): δ 7.36 (d, 3JH-H = 8 Hz, 2H, CH tol), 6.94 (d, 3JH-H = 7 Hz, 2H, CH Ph), 6.63 (m, 3H, CH Ph), 6.54 (d, 3JH-H = 8 Hz, 2H, CH tol), 1.81 (s, 3H, CH3 tol). 11B{1H} NMR (128 MHz, tol-d8, 25 °C): δ 42.00. 19F (376 MHz, tol-d8, 25 °C): δ –131.42 (br, 4F, o-F (C6F5)), –131.62 (br, 4F, o-F (C6F5)), –150.95 (t, 3JF-F = 18 Hz, 2F, p-F (C6F5)), –151.59 (t, 3JF-F = 18 Hz, 2F, p-F (C6F5)), –161.06 (br, 4F, m-F (C6F5)), –131.42 (br, 4F, m-F (C6F5)). HRMS (EI-TOF) m/z: [M]+ Calcd for C25H12BF10NO2S 591.0522, Found 591.0529.
Aminoboranes of the general formula (C6F5)2BNH(R), where R = Ts, Ms, Cls, Ns, can be generated by reacting equimolar amounts of the appropriate ylide with either (C6F5)2BCl or (C6F5)2BH. A sample preparation is provided below. Synthesis of (C6F5)2BNH(Ts) 2a: A 50 mL schlenk was charged with TsN=IPh (16.6 mg, 0.044 mmol) in pentane (10 mL) to form a white slurry. A solution of (C6F5)2BCl (16.9 mg, 0.044 mmol) was added to the schlenk flask. The resulting slurry was stirred overnight and the white insoluble solid was subsequently collected by filtration. The powder was then dissolved in CH2Cl2 and stored at – 35 °C to allow for the formation of clear, colourless crystals. Crystals suitable for X-ray diffraction were obtained from a CH2Cl2 solution for compounds 2a, b, d. (C6F5)2BNH(Ts) 4: 1H NMR (400 MHz, C6D6, 25 °C): δ 7.88 (s, 1H, NH), 7.74 (d, 3JH-H = 8 Hz, 2H, tol CH), 6.67 (d, 3JH-H = 8 Hz, 2H, tol CH), 1.84 (s, 3H, CH3). 11B{1H} NMR (128 MHz, C6D6, 25 °C): δ 34.4 (s). 19F (376 MHz, C6D6, 25 °C): δ – 136.07 (br, 2F, o-F (C6F5)), – 136.43 (br, 2F, o-F (C6F5)), – 151.24 (br, 1F, p-F (C6F5)), – 156.19 (br, 1F, p-F (C6F5)), – 165.07 (br, 2F, m-F (C6F5)), – 165.35 (br, 2F, m-F (C6F5)). HRMS (EI-TOF) m/z: [M]+ Calcd for C19H8BF10NO2S 515.0209, Found 515.0225. (C6F5)2BNH(Cls) 5: 1H NMR (400 MHz, C6D6, 25 °C): δ 7.46 (s, 1H, NH), 7.20 (d, 3JH-H = 9 Hz, 2H, CH Ph), 6.73 (d, 3JH-H = 8 Hz, 2H, CH Ph). 11B{1H} NMR (128 MHz, C6D6, 25 °C): δ 39.30 (br). 19F (376 MHz, C6D6, 25 °C): δ – 131.32 (s, 4F, oF (C6F5)), – 145.84 (br, 2F, p-F (C6F5)), – 149.90 (br, 2F, p-F (C6F5)), – 160.73 (br, 4F, m-F (C6F5)). HRMS (EITOF) m/z: [M]+ Calcd for C18H5BF10NO2S 534.9663, Found 534.9659. (C6F5)2BNH(Ms) 6: 1H NMR (400 MHz, tol-d8, 25 °C): δ 7.32 (s, 1H, NH), 2.26 (s, 3H, CH3). 11B{1H} NMR (128 MHz, tol-d8, 25 °C): δ 39.74 (br). 19F (376 MHz, tol-d8, 25 °C): δ – 131.54 (br, 2F, o-F (C6F5)), – 132.19 (br, 2F, o-F (C6F5)), – 146.09 (br, 1F, p-F (C6F5)), – 150.01 (br, 1F, p-F (C6F5)), – 160.30 (br, 2F, m-F (C6F5)), – 161.38 (br, 2F, m-F (C6F5)). HRMS (EI-TOF) m/z: [M]+ Calcd for C13H4BF10NO2S 438.9896, Found 438.9897. (C6F5)2BNH(Ns) 7: 1H NMR (400 MHz, C6D6, 25 °C): δ 7.35 (d, 3JH-H = 9 Hz, 2H, CH Ph), 7.23 (s, 1H, NH), 7.09 (d, 3JH-H = 8 Hz, 2H, CH Ph). 11B{1H} NMR (128 MHz, C6D6, 25 °C): δ 39.55 (br). 19F (376 MHz, C6D6, 25 °C): δ – 131.36 (s, 4F, oF (C6F5)), – 144.69 (br, p-F (C6F5)), – 149.25 (br, p-F (C6F5)), – 160.31 (br, 4F, m-F (C6F5)). HRMS (EI-TOF) m/z: [M]+ Calcd for C18H5BF10N2O4S 545.9903, Found 545.9904.
Compound
31
P (ppm)
Δδ (ppm)
(C5F5)2BN(H)(Ms)
79.79
28.32
(C5F5)2BN(H)(Ts)
80.16
28.69
(C5F5)2BN(H)(C6H4Cl)
80.52
29.05
(C5F5)2BN(H)(Ns)
80.66
29.19
1.77
7.38 7.36 7.16
6.53 6.51
(C6F5)2BN(Ts)(C6F5) 1 1H
40000
35000
30000
25000
20000
15000
10000
5000
14
13
12
11
10
9
8
7
2.92
2.00
1.83
0
6 f1 (ppm)
5
4
3
2
1
0
-1
-2
4500
-3.75
42.91
11B
4000
3500
3000
2500
2000
1500
1000
500
0
130
120
110
100
90
80
70
60
50
40 f1 (ppm)
30
20
10
0
-10
-20
-30
-40
-50
-159.06 -160.29 -161.09
-142.22 -146.72 -148.74 -150.04
-128.59 -131.37
19F
8000 7500 7000 6500 6000 5500 5000 4500 4000 3500 3000 2500 2000 1500 1000 500
-30
-40
-50
-60
-70
-80
-90
-100
-110
-120 -130 f1 (ppm)
-140
-150
1.97 2.15 1.97
2.02 0.97 1.11 0.99
1.86 2.18
0
-160
-500 -170
-180
-190
-200
-210
-220
0.67
1.87 1.83
7.65
6.68
(C6F5)2BN(Ts)(C6F5) · OPEt3 2 1H 1400 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100
14
13
12
11
10
9
8
7
6 f1 (ppm)
5
4
3
2
8.88
8.59
2.00
2.09
0
1
0
-1
-2
1.41
11B
45
40
35
30
25
20
15
10
5
0
90
80
70
60
50
40
30
20
10
0 f1 (ppm)
-10
-20
-30
-40
-50
-60
-70
-80
-90
-163.83 -164.10
-154.59 -156.70
-137.99
-133.42
19F
120
110
100
90
80
70
60
50
40
30
20
10
-40
-50
-60
-70
-80
-90
-100
-110
-120
-130 -140 f1 (ppm)
-150
5.74
1.03 1.87
1.85
2.09
0
-160
-170
-180
-190
-200
-210
-220
-230
80.74
31P 75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
-5 280
260
240
220
200
180
160
140
120
100
80
60
40
20 0 -20 f1 (ppm)
-40
-60
-80
-100 -120 -140 -160 -180 -200 -220 -240 -260 -280
1.81
2.08
6.94
(C6F5)2BN(Ph)Ts 3 1H 450
400
350
300
250
200
150
100
50
13
12
11
10
9
8
7
2.98
2.02 3.11 1.92
2.00
0
6
5 f1 (ppm)
4
3
2
1
0
-1
-2
11B 41.91
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5
90
80
70
60
50
40
30
20
10
0 f1 (ppm)
-10
-20
-30
-40
-50
-60
-70
-80
-90
140
-161.06 -161.70
-150.95 -151.59
-131.42 -131.62
19F
130
120
110
100
90
80
70
60
50
40
30
20
10
70
50
30
10
-10
-30
-50
-70 f1 (ppm)
-90
-110
-130
-150
0.96 0.97
0.46 0.47
90
1.00 1.00
0
-170
-190
-210
-230
0.34
1.79
7.81 7.49 7.47 7.16
6.66 6.64
(C6F5)2BNH(Ts) 4 1H 28000 26000 24000 22000 20000 18000 16000 14000 12000 10000 8000 6000 4000 2000
14
13
12
11
10
9
8
3.18
2.07
2.08
1.00
0
7
6 f1 (ppm)
5
4
3
2
38.98
11B
4500
4000
3500
3000
2500
2000
1500
1000
500
0
130
120
110
100
90
80
70
60
50
40 f1 (ppm)
30
20
10
0
-10
-20
-30
-40
-50
1
0
-1
-2
-160.40 -161.67
-150.90
-146.18
-131.24 -131.28
19F
9000
8000
7000
6000
5000
4000
3000
2000
1000
-50
-60
-70
-80
-90
-100
-110
-120 -130 f1 (ppm)
-140
4.16
-40
0.78
-30
0.71
4.00
0
-150
-160
-170
-180
-190
-200
-210
-220
1.22 1.13 1.13 0.77 0.75 0.73
7.35 7.11 7.08 7.04 6.64 6.61
(C6F5)2BNH(Cls) 5 1H 17000 16000 15000 14000 13000 12000 11000 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000
13
12
11
10
9
8
2.00
2.04
0.98
0
7
-1000 6 f1 (ppm)
5
4
3
2
1
0
-1
-2
3.15
38.96
11B
3500
3000
2500
2000
1500
1000
500
0
130
120
110
100
90
80
70
60
50
40 f1 (ppm)
30
20
10
0
-10
-20
-30
-40
-50
-160.76
-145.61
-149.74
-131.30 -131.33 -131.37
19F 2500 2400 2300 2200 2100 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100
-50
-60
-70
-80
-90
-100
-110
-120 -130 f1 (ppm)
-140
4.09
-40
0.62
-30
0.60
4.00
0
-150
-160
-100 -170
-180
-190
-200
-210
-220
2.28
7.22
(C6F5)2BNH(Ms) 6 1H 2600
2400
2200
2000
1800
1600
1400
1200
1000
800
600
400
200
14
13
12
11
10
9
8
3.00
0.97
0
7
6 f1 (ppm)
5
4
3
2
1
0
-1
-2
11B 39.84
30
28
26
24
22
20
18
16
14
12
10
8
6
4
2
0
90
80
70
60
50
40
30
20
10
0 f1 (ppm)
-10
-20
-30
-40
-50
-60
-70
-80
-90
-160.87
-146.22 -150.36
-131.90
130
120
110
100
90
80
70
60
50
40
30
20
10
19F
90
70
50
30
10
-10
-30
-50
-70 f1 (ppm)
-90
-110
-130
-150
3.96
0.97 0.77
4.00
0
-170
-190
-210
-230
7.48 7.46 7.35 7.23 7.21 7.16
1.26 0.89 0.87 0.86
(C6F5)2BNH(Ns) 7 1H 12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
2000
1000
1.86 0.92 2.00
0
14
13
12
11
10
9
8
7
6 f1 (ppm)
5
4
3
2
1
0
-1
-2
39.13
11B
40
35
30
25
20
15
10
5
0
90
80
70
60
50
40
30
20
10
0 f1 (ppm)
-10
-20
-30
-40
-50
-60
-70
-80
-90
7.48 7.46 7.35 7.23 7.21 7.16
1.26 0.89 0.87 0.86
1H
12000
11000
10000
9000
8000
7000
6000
5000
4000
3000
2000
1000
1.86 0.92 2.00
0
14
13
12
11
10
9
8
7
6 f1 (ppm)
5
4
3
2
1
0
-1
-2
