Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information Syntheses and structures of copper complexes of 3-(6-(1H-pyrazol-1-yl)pyridin-2-yl)pyrazol-1-ide and their excellent performance in the syntheses of nitriles and aldehydes Da-Wei Tan, a Jing-Bo Xie, a Qi Li, a Hong-Xi Li, a, * Jun-Chi Li, a Jian-Ping Lang a,b * a College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 210032, P. R. China S1
Table of Contents Figure S1. One-dimensional chain (extended along the b axis) formed via H-bonding interactions in 4. S4 Figure S2. The calculated isotope pattern (top) and the observed patterns (below) of the [{(Cu(NO 3 ))(μ-pzpypz)} 2 + NO 3 + 2CH 3 CN] + cation in the positive-ion ESI mass spectrum of 1. S4 Figure S3. The calculated isotope pattern (top) and the observed patterns (below) of the [CuClO 4 (pzpypzh)cuoch 3 (pzpypz)] + cation in the positive-ion ESI mass spectrum of 2. S4 Figure S4. The calculated isotope pattern (top) and the observed patterns (below) of the [{Cu 2 (μ-so 4 )(μ-pzpypz) 2 } + HSO 4 + 2MeOH + 4H 2 O + CH 3 CN] + cation in the positive-ion ESI mass spectrum of 3. S5 Figure S5. The calculated isotope pattern (top) and the observed patterns (below) of the [{(CuI)(μ-pzpypz)} 2 + I + 3H 2 O + 4CH 3 CN] + cation in the positive-ion ESI mass spectrum of 5. S5 The 1 H and 13 C NMR data of benzonitrile, 2-methylbenzonitrile, 3-methylbenzonitrile, 4-methylbenzonitrile, 2-methoxybenzonitrile, 3-methoxybenzonitrile, 4-methoxybenzonitrile, 4-chlorobenzonitrile, 4-nitrobenzonitrile, 3,4-(methylenedioxy)benzonitrile, 1-naphthonitrile, 3-cyanopyridine, 2-thiophenecarbonitrile, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 4-chlorobenzoic aldehyde, 4-nitrobenzaldehyde, 3-pyridinecarboxaldehyde, 2-thenaldehyde S6 The 1 H and 13 C NMR spectra of 1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)ethanone S8 The 1 H and 13 C NMR spectra of 1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)-3-(dimethylamino)prop- 2-en-1-one S9 The 1 H and 13 C NMR spectra of 2-(1H-pyrazol-1-yl)-6-(1H-pyrazol-3-yl)pyridine S10 The 1 H and 13 C NMR spectra of the product benzonitrile S11 The 1 H and 13 C NMR spectra of the product 2-methylbenzonitrile S12 The 1 H and 13 C NMR spectra of the product 3-methylbenzonitrile S13 The 1 H and 13 C NMR spectra of the product 4-methylbenzonitrile S14 The 1 H and 13 C NMR spectra of the product 2-methoxybenzonitrile S15 The 1 H and 13 C NMR spectra of the product 3-methoxybenzonitrile S16 The 1 H and 13 C NMR spectra of the product 4-methoxybenzonitrile S17 S2
The 1 H and 13 C NMR spectra of the product 4-chlorobenzonitrile S18 The 1 H and 13 C NMR spectra of the product 4-nitrobenzonitrile S19 The 1 H and 13 C NMR spectra of the product 1-naphthonitrile S20 The 1 H and 13 C NMR spectra of the product 3,4-(methylenedioxy)benzonitrile S21 The 1 H and 13 C NMR spectra of the product 3-cyanopyridine S22 The 1 H and 13 C NMR spectra of the product 2-thiophenecarbonitrile S23 The 1 H and 13 C NMR spectra of the product benzaldehyde S24 The 1 H and 13 C NMR spectra of the product 2-methylbenzaldehyde S25 The 1 H and 13 C NMR spectra of the product 3-methylbenzaldehyde S26 The 1 H and 13 C NMR spectra of the product 4-methylbenzaldehyde S27 The 1 H and 13 C NMR spectra of the product 2-methoxybenzaldehyde S28 The 1 H and 13 C NMR spectra of the product 3-methoxybenzaldehyde S29 The 1 H and 13 C NMR spectra of the product 4-methoxybenzaldehyde S30 The 1 H and 13 C NMR spectra of the product 4-chlorobenzoic aldehyde S31 The 1 H and 13 C NMR spectra of the product 4-nitrobenzaldehyde S32 The 1 H and 13 C NMR spectra of the product 3-pyridinecarboxaldehyde S33 The 1 H and 13 C NMR spectra of the product 2-thenaldehyde S34 S3
Figure S1. One-dimensional chain (extended along the b axis) formed via H-bonding interactions in 4. 690.06 690 691 692 693 694 695 696 m/z Figure S2. The calculated isotope pattern (top) and the observed patterns (below) of the [{(Cu(NO 3 ))(μ-pzpypz)} 2 + NO 3 + 2CH 3 CN] + cation in the positive-ion ESI mass spectrum of 1. 773.07 774 776 778 m/z Figure S3. The calculated isotope pattern (top) and the observed patterns (below) of the [CuClO 4 (pzpypzh)cuoch 3 (pzpypz) + 3MeOH] + cation in the positive-ion ESI mass spectrum of 2. S4
756.04 756 757 758 759 760 761 m/z Figure S4. The calculated isotope pattern (top) and the observed patterns (below) of the [{Cu 2 (μ-so 4 )(μ-pzpypz) 2 } + HSO 4 + 2MeOH + 4H 2 O + CH 3 CN] + cation in the positive-ion ESI mass spectrum of 3. 893.06 891 892 893 894 895 896 m/z Figure S5. The calculated isotope pattern (top) and the observed patterns (below) of the [{(CuI)(μ-pzpypz)} 2 + I + 3H 2 O + 4CH 3 CN] + cation in the positive-ion ESI mass spectrum of 5. S5
benzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.47 (t, J = 8.0Hz, 1H), 7.60 (d, J = 8.0Hz, 1H), 7.64 (d, J = 8.0Hz, 2H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 112.2, 118.6, 128.9, 132.0, 132.6. 2-methylbenzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 2.53 (s, 3H), 7.26 (d, J = 8.0Hz, 1H), 7.31 (t, J = 8.0Hz, 1H), 7.47 (t, J = 8.0Hz, 1H), 7.56 (d, J = 8.0Hz, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 20.2, 112.4, 117.9, 126.0, 130.0, 132.2, 132.4, 141.6. 3-methylbenzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 2.37 (s, 3H), 7.34 (t, J = 8.0Hz, 1H), 7.41 (t, J = 8.0Hz, 3H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 20.8, 111.8, 118.7, 128.7, 132.1, 133.4, 138.8. 4-methylbenzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 2.42 (s, 3H), 7.27 (d, J = 8.0Hz, 2H), 7.52 (d, J = 8.0Hz, 2H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 21.7, 109.1, 119.0, 129.7, 131.9, 143.6. 2-methoxybenzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 2.53 (s, 3H), 7.27 (t, J = 8.0Hz, 1H), 7.31 (t, J = 8.0Hz, 1H), 7.48 (t, J = 8.0Hz, 1H), 7.57 (t, J = 8.0Hz, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 20.2, 112.4, 117.9, 126.0, 130.0, 132.2, 132.4, 141.6. 3-methoxybenzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 3.83 (s, 3H), 7.13 (d, J = 8.0Hz, 2H), 7.23 (d, J = 8.0Hz, 1H), 7.37 (t, J = 8.0Hz, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 55.3, 112.9, 116.6, 118.6, 119.1, 124.2, 130.1, 159.4. 4-methoxybenzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 3.86 (s, 3H), 6.95 (d, J = 8.0Hz, 2H), 7.58 (d, J = 8.0Hz, 2H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 55.5, 103.9, 114.7, 119.2, 133.9, 162.8. 4-chlorobenzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.47 (d, J = 8.0Hz, 2H), 7.61 (d, J = 8.0Hz, 2H). 13 C NMR (125 MHz, CDCl 3, ppm): δ 110.7, 117.9, 129.6, 133.3, 139.4. 4-nitrobenzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.89 (d, J = 8.0Hz, 2H), 8.35 (d, J = 8.0Hz, 2H). 13 C NMR (125 MHz, CDCl 3, ppm): δ 116.7, 118.2, 124.2, 133.4, 150.0. 3,4-(Methylenedioxy)benzonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 6.08 (s, 2H), 6.87 (d, J = 8.0Hz, 1H), 7.02 (s, 1H), 7.21 (d, J = 8.0Hz, 1H). 13 C NMR (125 MHz, CDCl 3, ppm): δ 102.1, 104.8, 109.0, 111.2, 118.8, 128.0, 147.9, 151.4. 1-naphthonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.47 (t, J = 8.0Hz, 1H), 7.58 (t, J = 8.0Hz, 1H), 7.64 (t, J = 8.0Hz, 1H), 7.86 (t, J = 8.0Hz, 2H), 8.02 (d, J = 8.0Hz, 1H), 8.19 (d, J = 8.0Hz, 1H). 13 C NMR (125 MHz, CDCl 3, ppm): δ 110.0, 117.8, 124.8, 127.3, 128.4, 128.5, 132.1, 132.4, 132.7, 133.1. 3-cyanopyridine: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.49 (t, J = 8.0Hz, 1H), 8.02 (d, J = 8.0Hz, 1H), 8.86 (s, 1H), 8.92 (s, 1H). 13 C NMR (75 MHz, CDCl 3, ppm): δ 109.8, 116.3, 123.5, 139.1, 152.2, 152.7. 2-thiophenecarbonitrile: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.75 (s, 3H). 13 C NMR (100 MHz, CDCl 3, S6
ppm): δ 109.2, 113.9, 127.3, 132.4, 137.1 benzaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.50 (t, J = 8.0Hz, 2H), 7.60 (t, J = 8.0Hz, 1H), 7.86 (d, J = 8.0Hz, 2H), 9.99 (s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 129.1, 129.8, 134.6, 136.5, 192.5. 2-methylbenzaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 2.66 (s, 3H), 7.25 (d, J = 8.0Hz, 1H), 7.35 (t, J = 8.0Hz, 1H), 7.47 (t, J = 8.0Hz, 1H), 7.79 (d, J = 8.0Hz, 1H), 10.26 (s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 19.9, 126.3, 131.8, 132.1, 133.7, 134.2, 140.6, 192.8. 3-methylbenzaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 2.41 (s, 3H), 7.39 (t, J = 8.0Hz, 2H), 7.66 (s, 2H), 9.96 (s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 21.2, 127.2, 128.9, 130.0, 135.3, 136.5, 138.9, 192.6. 4-methylbenzaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 2.44 (s, 3H), 7.33 (d, J = 8.0Hz, 2H), 7.77 (t, J = 8.0Hz, 2H), 9.96 (s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 21.2, 71.8, 127.9, 129.1, 135.3, 137.3. 2-methoxybenzaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 3.89 (s, 3H), 6.95-7.01 (m, 2H), 7.53 (t, J = 8.0Hz, 1H), 7.80 (d, J = 8.0Hz, 1H), 10.45 (s, 1H). 13 C NMR (125 MHz, CDCl 3, ppm): δ 55.3, 111.4, 120.3, 124.5, 128.0, 135.7, 161.5, 189.4. 3-methoxybenzaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 3.06 (s, 3H), 7.13-7.16 (m, 1H), 7.33-7.43 (m, 3H), 9.94 (s, 1H). 13 C NMR (125 MHz, CDCl 3, ppm): δ 55.3, 112.0, 121.3, 123.3, 129.9, 137.7, 160.0, 191.9. 4-methoxybenzaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 3.73 (s, 3H), 6.86 (d, J = 12.0Hz, 2H), 7.69 (d, J = 12.0Hz, 2H), 9.73 (s, 1H). 13 C NMR (125 MHz, CDCl 3, ppm): δ 55.2, 114.0, 129.6, 131.6, 164.2, 190.4. 4-chlorobenzoic aldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.53 (d, J = 12.0Hz, 2H), 7.83 (d, J = 12.0Hz, 2H), 9.99 (s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 129.5, 130.9, 134.7, 141.0, 190.9. 4-nitrobenzaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 8.09 (d, J = 8.0Hz, 2H), 8.41 (d, J = 12.0Hz, 2H), 10.17(s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 124.3, 130.5, 140.1, 151.1, 190.4. 3-pyridinecarboxaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.51-7.54 (m, 1H), 8.20 (d, J = 8.0Hz, 1H), 8.87 (d, J = 8.0Hz, 1H), 9.11 (d, J = 4.0Hz, 1H), 10.15 (s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm): δ 124.0, 131.3, 135.7, 151.7, 154.5, 190.8. 2-thenaldehyde: 1 H NMR (400 MHz, CDCl 3, ppm): δ 7.21-7.24 (m, 1H), 7.77-7.80 (m, 2H), 9.96 (d, J = 4.0Hz, 1H). 13 C NMR (125 MHz, CDCl 3, ppm): δ 128.2, 134.9, 136.3, 143.7, 182.8. S7
The 1 H and 13 C NMR spectra of 1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)ethanone 199.0 151.6 150.5 142.3 139.6 126.9 115.9 108.1 77.4 77.0 76.6 25.6 S8
The 1 H and 13 C NMR spectra of 1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)-3-(dimethylamino)prop-2-en-1-one S9
The 1 H and 13 C NMR spectra of 2-(1H-pyrazol-1-yl)-6-(1H-pyrazol-3-yl)pyridine 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 f1 (ppm) 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 S10
The 1 H and 13 C NMR spectra of the product benzonitrile S11
The 1 H and 13 C NMR spectra of the product 2-methylbenzonitrile 0.98 1.00 1.00 0.97 3.05 7.58 7.56 7.49 7.48 7.46 7.32 7.30 7.28 7.26 7.24 2.53 S12
The 1 H and 13 C NMR spectra of the product 3-methylbenzonitrile 138.9 133.4 128.9 128.7 118.7 111.8 77.3 77.0 76.7 20.8 2.94 1.00 3.00 7.43 7.41 7.39 7.36 7.34 7.32 2.37 S13
The 1 H and 13 C NMR spectra of the product 4-methylbenzonitrile 143.6 131.9 129.7 119.0 109.1 77.3 77.0 76.7 21.7 1.91 1.98 3.00 7.54 7.52 7.28 7.26 2.42 S14
The 1 H and 13 C NMR spectra of the product 2-methoxybenzonitrile 160.8 134.2 133.3 120.5 116.2 111.1 101.1 S15
The 1 H and 13 C NMR spectra of the product 3-methoxybenzonitrile 159.4 130.1 124.2 119.1 118.6 116.6 112.9 77.3 77.0 76.7 55.3 0.97 0.93 1.87 3.00 7.39 7.37 7.35 7.29 7.24 7.22 7.14 7.12 3.83-0.00 S16
The 1 H and 13 C NMR spectra of the product 4-methoxybenzonitrile S17
The 1 H and 13 C NMR spectra of the product 4-chlorobenzonitrile 2.00 2.01 7.62 7.60 7.48 7.46 7.29-0.00 S18
The 1 H and 13 C NMR spectra of the product 4-nitrobenzonitrile 149.9 133.4 124.2 118.2 116.7 77.2 77.0 76.8 2.00 2.00 8.36 8.33 7.90 7.88 7.26-0.04 S19
The 1 H and 13 C NMR spectra of the product 1-naphthonitrile 1.00 1.03 2.10 1.04 1.06 1.13 8.20 8.18 8.03 8.01 7.89 7.86 7.84 7.66 7.64 7.62 7.60 7.58 7.56 7.49 7.47 7.45 7.26 0.01 S20
The 1 H and 13 C NMR spectra of the product 3,4-(methylenedioxy)benzonitrile 151.4 147.9 128.0 118.7 109.0 104.7 102.1 77.2 77.0 76.8 0.96 0.95 0.98 2.00 7.29 7.22 7.20 7.02 6.88 6.86 6.08-0.00 S21
The 1 H and 13 C NMR spectra of the product 3-cyanopyridine 1.00 1.00 1.00 1.02 8.92 8.86 8.85 8.03 8.01 7.51 7.49 7.48 7.33 S22
The 1 H and 13 C NMR spectra of the product 2-thiophenecarbonitrile 3.00 7.75 7.26 2- 氰基噻吩 - 碳谱 137.1 132.4 127.3 113.9 109.2 77.3 77.0 76.7 160 155 150 145 140 135 130 125 120 115 110 f1 (ppm) 105 100 95 90 85 80 75 70 S23
The 1 H and 13 C NMR spectra of the product benzaldehyde 1.00 2.03 1.01 2.00 9.99 7.87 7.85 7.62 7.60 7.58 7.52 7.50 7.48 7.30 tdw-2-c400 13C OBSERVE 192.5 136.5 134.6 129.8 129.1 77.8 77.5 77.2 230 210 190 170 150 130 110 f1 (ppm) 90 80 70 60 50 40 30 20 10 0 S24
The 1 H and 13 C NMR spectra of the product 2-methylbenzaldehyde 0.92 0.98 1.02 0.95 0.97 3.00 10.26 7.80 7.78 7.49 7.47 7.45 7.37 7.35 7.33 7.26 7.24 2.66 邻甲基苯甲醛 - 碳谱 210 190 170 150 130 110 90 f1 (ppm) 80 70 60 50 40 30 20 10 0 S25
The 1 H and 13 C NMR spectra of the product 3-methylbenzaldehyde 192.6 138.9 136.5 135.3 130.0 128.9 127.2 77.4 77.0 76.7 21.2 1.00 2.01 1.99 3.09 9.96 7.66 7.65 7.41 7.39 7.37 2.41 S26
The 1 H and 13 C NMR spectra of the product 4-methylbenzaldehyde 137.3 135.3 129.1 127.9 77.4 77.0 76.7 71.8 21.2 0.97 1.98 1.99 3.00 9.96 7.78 7.76 7.34 7.32 7.25 2.44 S27
The 1 H and 13 C NMR spectra of the product 2-methoxybenzaldehyde 1.00 1.00 0.99 1.97 2.99 10.45 7.81 7.79 7.55 7.53 7.51 7.30 7.01 6.99 6.97 6.95 3.89 S28
The 1 H and 13 C NMR spectra of the product 3-methoxybenzaldehyde CARBON_01 191.9 160.0 137.7 129.9 123.3 121.3 112.0 77.2 77.0 76.8 55.3 240 220 200 180 160 140 120 100 f1 (ppm) 80 60 40 20 0 S29
The 1 H and 13 C NMR spectra of the product 4-methoxybenzaldehyde 1.00 1.03 0.92 1.08 0.91 3.05 9.73 7.70 7.67 7.22 6.87 6.84 3.73 CARBON_01 190.4 164.2 131.6 129.6 114.0 77.2 77.0 76.8 55.2 240 220 200 180 160 140 120 100 f1 (ppm) 80 60 40 20 0 S30
The 1 H and 13 C NMR spectra of the product 4-chlorobenzoic aldehyde 1.00 1.97 1.95 9.99 7.84 7.82 7.53 7.51 7.26 S31
The 1 H and 13 C NMR spectra of the product 4-nitrobenzaldehyde 190.4 151.1 140.1 130.5 124.3 77.4 77.1 76.8 1.00 2.02 2.00 10.17 8.42 8.39 8.10 8.08 7.27 S32
The 1 H and 13 C NMR spectra of the product 3-pyridinecarboxaldehyde S33
The 1 H and 13 C NMR spectra of the product 2-thenaldehyde S34