Organometallics
Article
1
29.0, 127.8, 126.8, 126.6, 125.5, 120.8, 120.7, 120.0, 53.4, 22.6, 22.3.
8.66 (s, 2H), 8.57 (d, J = 4.0 Hz, 2H), 8.50 (d, J = 8.8 Hz, 2H), 8.42
(d, J = 8.8 Hz, 2H), 7.95 (s, 2H), 7.91 (dd, J = 4.8 Hz, J = 4.8 Hz, 2H),
7.25 (t, J = 8.0 Hz, 2H), 7.13 (d, J = 7.6 Hz, 2H), 6.88 (d, J = 8.0 Hz,
2H), 1.79 (m, 2H, CH(CH ) ), 1.63 (m, 2H, CH(CH ) ), 1.00 (d, J =
Anal. Calcd for C H Cu F N P : C, 43.51; H, 3.25; N, 11.28.
Found: C, 43.51; H, 3.23; N, 11.08.
Cu (L5) ](PF ) , 5. This complex was synthesized from [HL5](PF )
36
32
2
12
8 2
[
2
2
6 2
6
3
2
3 2
(
90 mg, 0.20 mmol) and Cu powder (32 mg, 0.50 mmol). Yield: 52
6.4 Hz, 6H, CH ), 0.24 (d, J = 6.4 Hz, 6H, CH ), 0.05 (d, J = 6.8 Hz,
3
3
1
13
mg (51%), red powder. H NMR (400 MHz, DMSO-d ): δ 9.26 (d, J
=
6H, CH ), −0.61 (d, J = 6.0 Hz, 6H, CH ). C NMR (100 MHz,
6
3
3
8.8 Hz, 1.6H), 9.23 (d, J = 8.8 Hz, 1H), 8.83 (d, J = 8.4 Hz, 1.6H),
DMSO-d ): δ 177.6 (Cu-C), 148.7, 146.8, 145.0, 142.8, 142.0, 141.7,
6
8
2
1
9
.66 (d, J = 4.4 Hz, 1.6H), 8.61 (d, J = 8.4 Hz, 1H), 8.53−8.58 (m,
.6H), 8.50 (s, 1H), 8.43 (d, J = 8.8 Hz, 1.6H), 8.35 (d, J = 9.2 Hz,
.6H), 8.30 (d, J = 9.6 Hz, 2.6H), 8.18 (d, J = 4.4 Hz, 1H), 8.14 (d, J =
.2 Hz, 1H), 8.08 (s, 1H), 7.89 (dd, J = 4.8 Hz, J = 4.4 Hz, 1.6H), 7.71
138.2, 134.2, 130.0, 129.4, 127.6, 127.1, 126.8, 125.8, 124.3, 123.0,
121.8, 120.8, 27.5, 27.5, 23.8, 23.6, 22.7, 19.5. Anal. Calcd for
C H Cu F N P (7·0.5CH CN): C, 52.82; H, 4.31; N, 9.52.
5
5
53.5
2
12 8.5
2
3
Found: C, 52.40; H, 4.32; N, 9.51.
(
1
s, 1.6H), 7.63 (dd, J = 4.8 Hz, J = 4.8 Hz, 1H), 1.39 (s, 9H), 0.80 (s,
[Cu (L8) ](PF ) , 8. This complex was synthesized from [HL8](PF )
2
2
6 2
6
4.4H). 13C NMR (100 MHz, DMSO-d ): δ 177.4 (Cu-C), 173.9
(113 mg, 0.20 mmol) and Cu powder (32 mg, 0.50 mmol). Yield: 91
6
1
(
Cu-C), 150.4, 150.1, 149.3, 148.3, 142.6, 142.0, 141.8, 141.3, 141.1,
mg (73%), red powder. H NMR (400 MHz, DMSO-d ): δ 9.00 (d, J
6
1
1
39.1, 137.8, 129.3, 128.9, 128.5, 127.9, 127.3, 127.0, 126.5, 125.7,
25.6, 122.1, 121.5, 120.7, 120.3, 120.1, 57.7, 57.3, 29.8, 29.4. Anal.
= 8.0 Hz, 2H), 8.59 (d, J = 8.0 Hz, 2H), 8.31 (d, J = 7.2 Hz, 2H),
8.20−8.26 (m, 4H), 8.12 (d, J = 8.8 Hz, 2H), 8.08 (d, J = 4.0 Hz, 2H),
7.99 (s, 2H), 7.62−7.69 (m, 4H), 7.23−7.29 (m, 6H), 7.04−7.13 (m,
4H), 5.25−5.34 (m, 4H), 5.21 (d, J = 16.0 Hz, 2H), 5.05 (d, J = 15.6
Calcd for C H Cu F N P : C, 44.67; H, 3.55; N, 10.97. Found: C,
38
36
2
12
8 2
4
4.73; H, 3.52; N, 11.14.
Cu (L6) ](PF ) , 6a. This complex was synthesized from [HL6]-
Hz, 2H). 13C NMR (100 MHz, DMSO-d ): δ 181.5 (Cu-C), 149.1,
[
2
2
6 2
6
(
PF ) (102 mg, 0.20 mmol) and Cu powder (32 mg, 0.50 mmol).
148.9, 142.1, 141.6, 141.0, 140.9, 137.8, 135.1, 128.8, 128.6, 128.2,
127.8, 127.7, 126.7, 126.3, 125.1, 123.7, 119.6, 119.2, 52.8, 44.9. Anal.
Calcd for C H Cu F N O P (8·Et O·H O): C, 48.25; H, 3.75; N,
6
1
Yield: 89 mg (78%), red powder. H NMR (400 MHz, DMSO-d ): δ
6
9
.28 (d, J = 8.0 Hz, 1H), 9.17 (d, J = 8.0 Hz, 1H), 8.96 (s, 1H), 8.83
54
50
2
12 14
2
2
2
2
(
m, 2H), 8.73 (s, 1H), 8.53−8.65 (m, 4H), 8.46 (d, J = 8.4 Hz, 1H),
14.59. Found: C, 47.92; H, 3.45; N, 14.29.
[Cu (L9) ](PF ) , 9. This complex was synthesized from [HL9](PF )
8
1
1
3
.37 (d, J = 8.8 Hz, 1H), 8.32 (d, J = 8.4 Hz, 1H), 8.26 (d, J = 8.0 Hz,
H), 7.92 (m, 2H), 7.86 (s, 1H), 7.65 (s, 1H), 6.89 (s, 1H), 6.51 (s,
H), 6.13 (s, 1H), 5.85 (s, 1H), 2.09 (s, 3H), 1.66 (s, 3H), 1.59 (s,
H), 1.57 (s, 3H), 1.48 (s, 3H), 0.39 (s, 3H). 13C NMR (100 MHz,
2
2
6 2
6
(87 mg, 0.20 mmol) and Cu powder (32 mg, 0.50 mmol). Yield: 64
1
mg (65%), yellow powder. H NMR (400 MHz, DMSO-d ): δ 9.20−
6
9.26 (m, 4H), 8.73 (d, J = 8.0 Hz, 2H), 8.63 (d, J = 8.8 Hz, 2H), 8.56
(d, J = 4.4 Hz, 2H), 8.39 (d, J = 8.8 Hz, 2H), 8.25 (d, J = 8.4 Hz, 2H),
7.78 (dd, J = 4.8 Hz, J = 4.8 Hz, 2H), 5.48 (m, 2H, CH CHCH ),
DMSO-d ): δ 181.2 (Cu-C), 177.6 (Cu-C), 150.3, 149.0, 148.5, 147.2,
6
1
1
1
2
5
42.1, 141.7, 141.4, 141.1, 138.9, 138.7, 138.3, 138.1, 135.4, 134.5,
34.0, 133.7, 133.1, 129.5, 129.3, 128.8, 128.7, 128.4, 127.7, 127.4,
26.9, 126.5, 125.9, 125.3, 124.6, 121.5, 121.0, 120.2, 118.7, 118.7,
0.2, 19.8, 17.1, 16.8, 16.7, 14.2. Anal. Calcd for C H Cu F N P : C,
2
2
13
4.62−4.85 (m, 8H, CH CHCH ). C NMR (100 MHz, DMSO-
2
2
d ): δ 181.0 (Cu-C), 150.7, 149.3, 145.7, 142.6, 142.3, 141.2, 138.9,
6
48
40
2
12
8
2
132.1, 129.1, 128.3, 127.3, 126.6, 125.6, 119.5, 119.0, 50.4. Anal. Calcd
0.31; H, 3.52; N, 9.78. Found: C, 50.23; H, 3.69; N, 10.16.
Cu (μ-Cl)(L6) ]Cl, 6b. This complex was synthesized from
for C H Cu F N OP (9·H O): C, 40.45; H, 2.80; N, 13.87.
34
28
2
12 10
2
2
[
Found: C, 40.79; H, 2.53; N, 13.64.
2
2
imidazolium salt [HL6]Cl (80 mg, 0.20 mmol) and Cu powder (32
mg, 0.50 mmol). Yield: 89 mg (96%), red powder. H NMR (400
[Cu (L10) (μ-MeCN)](PF ) , 10. This complex was synthesized from
2
2
6 2
1
[HL10](PF ) (97 mg, 0.20 mmol) and Cu powder (32 mg, 0.50
6
1
MHz, DMSO-d ): δ 8.99 (m, 2H), 8.83 (m, 2H), 8.62 (m, 2H), 8.44
mmol). Yield: 110 mg (97%), red powder. H NMR (400 MHz,
6
(
(
s, 2H), 8.36 (m, 2H), 8.12 (m, 4H), 7.86 (m, 2H), 7.55 (s, 2H), 5.69
DMSO-d ): δ 9.36 (s, 2H), 9.20 (d, J = 8.8 Hz, 2H), 8.67 (q, J = 8.0
6
s, 4H), 1.71 (s, 6H), 1.47 (s, 6H), 1.28 (s, 6H). 13C NMR (100 MHz,
Hz, 4H), 8.46 (s, 2H), 8.36 (d, J = 8.8 Hz, 2H), 8.23 (d, J = 8.4 Hz,
DMSO-d ): δ 182.9 (Cu-C), 149.1, 148.2, 141.8, 141.3, 140.0, 136.8,
2H), 7.75 (m, 2H), 6.80 (m, 4H), 6.55 (m, 6H), 5.39 (d, J = 14.8 Hz,
6
13
1
1
6
35.8, 133.9, 133.5, 128.9, 127.4, 126.5, 125.8, 124.4, 123.4, 121.8,
19.0, 118.9, 19.9, 17.4, 16.8. Anal. Calcd for C H Cl Cu N : C,
2H), 5.05 (d, J = 14.8 Hz, 2H), 2.06 (s, 3H, CH CN). C NMR (100
3
48
40
2
2
8
MHz, DMSO-d ): δ 180.1 (Cu-C), 150.5, 149.3, 146.1, 142.5, 142.0,
6
2.20; H, 4.35; N, 12.09. Found: C, 62.17; H, 4.50; N, 12.24.
Cu (μ-Br)(L6) ]Br, 6c. This complex was synthesized from [HL6]Br
141.1, 138.8, 134.4, 129.1, 128.2, 127.8, 127.5, 127.2, 126.5, 125.5,
119.4, 117.9, 51.6, 1.0. Anal. Calcd for C H Cu F N P : C, 46.65;
[
2
2
44 33
2 12 11 2
(
89 mg, 0.20 mmol) and Cu powder (32 mg, 0.50 mmol). Yield: 95
H, 2.94; N, 13.60. Found: C, 46.82; H, 2.84; N, 13.33.
[Cu (L11) (MeCN) ](PF ) , 11. This complex was synthesized from
1
mg (93%), red powder. H NMR (400 MHz, DMSO-d ): δ 9.00 (d, J
6
3
4
2
6 3
=
(
8.8 Hz, 2H), 8.83 (d, J = 4.0 Hz, 2H), 8.62 (d, J = 7.6 Hz, 2H), 8.43
s, 2H), 8.40 (d, J = 8.8 Hz, 2H), 8.17 (q, J = 8.8 Hz, 4H), 7.87 (dd, J
4.8 Hz, J = 4.4 Hz, 2H), 7.55 (s, 2H), 5.70 (s, 4H), 1.71 (s, 6H,
[HL11](PF ) (79 mg, 0.20 mmol) and Cu powder (32 mg, 0.50
6
1
mmol). Yield: 43 mg (51%), red powder. H NMR (400 MHz,
=
DMSO-d ): δ 8.92−9.07 (m, 12H), 8.75−8.86 (m, 4H), 8.47−8.59
6
13
CH ), 1.47 (s, 6H, CH ), 1.28 (s, 6H, CH ). C NMR (100 MHz,
(m, 4H), 8.19−8.35 (m, 8H), 7.93−8.06 (m, 4H), 7.55−7.85 (m, 4H),
3
3
3
DMSO-d ): δ 182.6 (Cu-C), 149.2, 148.3, 141.7, 141.1, 140.1, 136.8,
6.35−6.57 (m, 4H), 2.08 (s, 6H, CH CN). Anal. Calcd for
6
3
1
1
35.9, 135.8, 134.2, 133.6, 128.9, 127.5, 126.7, 126.6, 126.3, 125.9,
24.5, 123.5, 122.1, 119.2, 19.9, 17.7, 16.7. Anal. Calcd for
C H Cu F N P : C, 45.41; H, 2.74; N, 14.89. Found: C, 45.64;
6
4
46
3 18 18 3
13
H, 2.57; N, 14.76. A satisfactory C NMR spectrum of 11 was not
obtained.
C H Br Cu N : C, 56.64; H, 4.16; N, 11.01. Found: C, 56.51; H,
4
8
42
2
2
8
4
.21; N, 11.14.
Cu (μ-I)(L6) ]I, 6d. This complex was synthesized from [HL6]I (99
[Cu(HL12) ](PF ) , 12. This complex was synthesized from
2
6 3
[
[HL12](PF ) (90 mg, 0.20 mmol) and Cu powder (32 mg, 0.50
2
2
6
1
mg, 0.20 mmol) and Cu powder (32 mg, 0.50 mmol). Yield: 108 mg
mmol). Yield: 85 mg (77%), red powder. H NMR (400 MHz,
1
(
97%), red powder. H NMR (400 MHz, DMSO-d ): δ 9.00 (d, J =
DMSO-d ): δ 9.27 (d, J = 5.6 Hz, 2H), 8.93−9.06 (m, 4H), 8.46−8.53
6
6
8
4
7
6
1
1
1
5
.8 Hz, 2H), 8.87 (s, 2H), 8.61 (d, J = 7.6 Hz, 2H), 8.39−8.46 (m,
(m, 4H), 8.41 (d, J = 7.2 Hz, 2H), 8.07−8.19 (m, 2H), 7.59−7.68 (m,
2H), 6.71−6.83 (m, 2H), 5.46−5.64 (m, 2H, CH CHCH ), 5.28
H), 8.18 (q, J = 8.8 Hz, 4H), 7.86 (dd, J = 4.8 Hz, J = 4.8 Hz, 2H),
2
2
.56 (s, 2H), 5.71 (s, 2H), 5.68 (s, 2H), 1.72 (s, 6H, CH ), 1.46 (s,
(d, J = 10.0 Hz, 2H, CH CHCH ), 5.19 (d, J = 18.0 Hz, 2H,
3
2
2
13
H, CH ), 1.27 (s, 6H, CH ). C NMR (100 MHz, DMSO-d ): δ
CH CHCH ), 4.23−4.55 (m, 4H, CH CHCH ), 3.33 (s, 6H,
CH ). C NMR (100 MHz, DMSO-d ): δ 149.8, 145.3, 144.2, 142.4,
3 6
3
3
6
2 2 2 2
13
82.3 (Cu-C), 149.4, 148.5, 141.6, 140.8, 140.2, 136.9, 135.9, 135.7,
34.2, 133.6, 129.0, 127.7, 126.9, 126.6, 126.3, 125.9, 124.5, 123.6,
22.5, 119.4, 19.9, 17.7, 16.7. Anal. Calcd for C H Cu I N : C,
142.3, 142.0, 138.2, 129.8, 129.6, 128.8, 127.0, 126.7, 126.5, 123.1,
48
40
2 2
8
121.6, 120.7, 49.7, 9.8. Anal. Calcd for C H CuF N P : C, 41.45; H,
38 34
18
8 3
1.95; H, 3.63; N, 10.10. Found: C, 51.93; H, 3.77; N, 10.26.
Cu (L7) ](PF ) , 7. This complex was synthesized from [HL7](PF )
3.11; N, 10.18. Found: C, 41.39; H, 3.04; N, 10.32.
[
General Procedure for the Copper-Catalyzed CuAAC
Reaction. Azide (1.0 mmol), alkyne (1.1 mmol), 3.0 mL of
CH CN, and 200 μL of the CH CN solution of complex 6b (2.5 ×
2
2
6 2
6
(
111 mg, 0.20 mmol) and Cu powder (32 mg, 0.50 mmol). Yield: 111
1
mg (90%), purple powder. H NMR (400 MHz, DMSO-d ): δ 9.35
6
3
3
−3
(
d, J = 8.4 Hz, 2H), 8.87 (d, J = 8.0 Hz, 2H), 8.73 (d, J = 8.8 Hz, 2H),
10 M) were added to a 10 mL Schlenk with a magnetic stirrer bar.
I
dx.doi.org/10.1021/om400738c | Organometallics XXXX, XXX, XXX−XXX