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Dalton Transactions
Page 10 of 13
ARTICLE
Journal Name
(neat, cm–1): 2918, 2850, 1600, 1560, 1505, 1410, 1331, 1225, 1160, before purifying by column chromatography. Then column
1090, 1045, 975, 810, 775, 726, 560; 1H NMR (500 MHz, chromatography on neutral alumina was performed using (10–15%)
DOI: 10.1039/C8DT04540B
DCM/ hexane as eluent.
CDCl3,ppm): 7.63 (s, 2H, -pyrrolic-H), 7.47 (dd, J = 3, 5.5 Hz, 2H,
Ar-H), 7.13 (m, 2H, Ar-H), 6.56 (d, J = 4 Hz, 2H, -pyrrolic-H), 6.39
(dd, J = 1, 3.5 Hz, 2H, -pyrrolic-H); 13C NMR (125.7 MHz, CDCl3,
ppm): 143.7, 140.9, 140.6, 133.3, 132.5, 132.5, 128.5, 117.7,
114.8, 114.6; ESI-MS: C15H12FN2+ [M+H]+: calcd m/z 239.0985, found
m/z 239.0911.
Compound Re1: General synthesis was followed. The desired
compound was purified by neutral alumina column using 20%
DCM/hexane mixture. Yield: (66.00 mg, 88%); m.p. 191 °C; IR (neat,
cm–1): 2923, 2852, 2020 (CO), 1926 (CO), 1896 (CO), 1604, 1548,
1495, 1452, 1379, 1242, 1033, 995, 726, 693; 1H NMR (500 MHz,
CDCl3,ppm): 8.17 (d, J = 7.5 Hz, 2H, Ar-H), 7.75 (s, 2H,-pyrrolic-
H), 7.60 (m, 2H, Ar-H), 7.5 (m, 5H, Ar-H), 7.34 (m, 5H, Ar-H), 7.26 (m,
6H, Ar-H), 6.95 (m, 6H, Ar-H), 6.73 (d, J = 8 Hz, 1H, Ar-H), 6.55 (d, J =
4 Hz, 2H, -pyrrolic-H), 6.37 (d, J = 4 Hz, 2H, -pyrrolic-H); 13C NMR
(125.7 MHz, CDCl3, ppm): 196.3, 154.5, 146.7, 140.7, 137.6, 136.6,
133.5, 133.5, 131.7, 131.2, 130.9, 130.6, 130.0, 128.4, 128.3, 126.0,
125.6, 125.2, 123.5, 120.4, 120.2, 118.9, 109.7; 31P NMR (202.4
MHz, CDCl3, ppm): 11.40; ESI-MS: C48H34N3O3PRe+ [M+H]+: calcd
m/z 918.1895, found m/z 918.1787.
Compound 6: General synthesis was performed. The desired
compound was purified by neutral alumina column using 40%
DCM/hexane mixture. Yield: (107.00 mg, 36%); m.p. 94 °C; IR (neat,
cm–1): 2931, 2857, 1610, 1585, 1565, 1485, 1385, 1228, 1119, 1095,
1
1005, 1045, 880, 775, 719, 520; H NMR (500 MHz, CDCl3, ppm):
7.65 (s, 2H, -pyrrolic-H), 7.41 (d, J = 7 Hz, 1H, Ar-H), 7.27 (d, J = 8
Hz, 1H, Ar-H), 7.21 (m, 2H, Ar-H), 6.58 (d, J = 4 Hz, 2H, -pyrrolic-H),
6.40 (d, J = 4Hz, 2H, -pyrrolic-H); 13C NMR (125.7 MHz, CDCl3,
ppm): 143.9, 140.6, 140.1, 139.4, 129.1, 128.5, 126.5, 117.8,
117.7, 117.6, 115.8, 115.7; ESI-MS: C15H12FN2+ [M+H]+: calcd m/z
239.0985, found m/z 239.0911.
Compound Re2: General synthesis was followed. The desired
compound was purified by neutral alumina column using 15%
DCM/hexane mixture. Yield: (63.12 mg, 86%); m.p. 171 °C; IR (neat,
cm–1): 2918, 2849, 2016 (CO), 1920 (CO), 1891 (CO), 1602, 1543,
1379, 1342, 1241, 1035, 995, 727, 694; 1H NMR (500 MHz,
CDCl3,ppm): 8.12 (s, 1H, Ar-H), 8.03 (d, J = 7.5 Hz, 1H, Ar-H), 7.71
(d, J = 15 Hz, 2H,-pyrrolic-H), 7.50-7.35 (m, 7H, Ar-H), 7.25 (m, 5H,
Ar-H), 7.11 (s, 1H, Ar-H), 6.96 (m, 6H, Ar-H), 6.65 (d, J = 7.5 Hz, 1H,
Ar-H), 6.47 (s, 2H, -pyrrolic-H), 6.29 (d, J = 6 Hz, 2H, -pyrrolic-H),
4.34 (t, J = 7Hz, 2H, N-CH2-C-), 1.92 (m, 2H, -C-CH2-C-), 1.48 (m, 2H, -
C-CH2-CH3), 0.99 (t, J = 7Hz, 3H, -C-CH3); 13C NMR (125.7 MHz, CDCl3,
ppm): 196.5, 153.8, 140.9, 140.2, 137.5, 133.6, 133.5, 132.3,
132.3, 131.0, 130.7, 129.9, 129.3,128.4, 128.3, 125.9, 122.6, 122.5,
122.6, 122.5, 122.1, 119.0, 118.4, 109.0, 107.0, 43.1, 31.2, 20.6,
13.9; 31P NMR (202.4 MHz, CDCl3, ppm): 10.68; MALDI-MS:
C46H38N303PRe+ [M+H]+: calcd m/z 898.0088, found m/z 898.440.
Compound 7: General synthesis was performed. The desired
compound was purified by neutral alumina column using 0.1%
methanol/DCM mixture. Yield: (218.00 mg, 73%); m.p. 151 °C; IR
(neat, cm–1): 2921, 2847, 1568, 1485, 1382, 1329, 1264, 1176, 1120,
1045, 1010, 935, 875, 795, 775, 720, 515; 1H NMR (500 MHz, CDCl3,
ppm): 7.6 (s, 2H, -pyrrolic-H), 7.59 (d, J = 8 Hz, 2H, Ar-H), 7.37 (d,
J = 8 Hz, 2H, Ar-H), 6.56 (d, J = 4 Hz, 2H, -pyrrolic-H), 6.41 (d, J = 4
Hz, 2H, -pyrrolic-H); 13C NMR (125.7 MHz, CDCl3, ppm): 143.9,
140.6, 140.3, 136.2, 132.3, 130.9, 128.8, 123.4, 117.8; ESI-MS:
C15H12BrN2+ [M+H]+: calcd m/z 299.0184, found m/z 299.0103.
Compound 8: General synthesis was followed. The desired
compound was purified by neutral alumina column using 50%
DCM/hexane mixture. Yield: (177.00 mg, 59%); m.p. 128 °C; IR
(neat, cm–1): 2921, 2850, 1547, 1379, 1338, 1225, 1115, 1090, 1039,
1
Compound Re3: General synthesis was followed. The desired
compound was purified by neutral alumina column using 18% DCM/
hexane mixture. Yield: (45.20 mg, 71%); m.p. 163 °C; IR (neat, cm–1):
2919, 2855, 2016 (CO), 1923 (CO), 1890 (CO), 1602, 1544, 1463,
1379, 1341, 1242, 1034, 994, 747, 695; 1H NMR (500 MHz,
CDCl3,ppm): 7.70 (bs, 2H, -pyrrolic-H), 7.35 (m, 3H, Ar-H), 7.19
(m, 8H, Ar-H), 6.92 (m, 7H, Ar-H), 6.81 (d, J = 8 Hz, 1H, Ar-H), 6.72
(d, J = 6.5 Hz, 1H, Ar-H), 6.50 (d, J = 4 Hz, 2H,-pyrrolic-H), 6.34 (d, J
= 7.5 Hz, 1H, Ar-H), 6.30 (bs, 2H,-pyrrolic-H), 6.10 (s, 1H, Ar-H),
3.88 (t, J = 7 Hz, 2H, N-CH2-C-), 1.84 (m, 2H, -C-CH2-C-), 1.47 (m, 2H,
-C-CH2-CH3), 0.98 (t, J = 7 Hz, 3H, -C-CH3); 13C NMR (125.7 MHz,
CDCl3, ppm): 196.5, 196.4, 190.20, 154.2, 154.1, 147.1, 145.2,
144.8, 136.7, 133.5, 133.4, 131.8, 130.8, 130.4, 130.0, 129.8, 129.3,
128.7, 128.4, 128.3, 127.5, 127.4, 124.4, 122.5, 118.5, 115.5, 113.6,
47.3, 29.1, 20.3, 13.8; 31P NMR (202.4 MHz, CDCl3, ppm): 10.76;
MALDI-MS: C46H38N303PReS+ [M+H]+: calcd m/z 930.1929, found
m/z 930.706.
985, 789, 702, 540, 460; H NMR (500 MHz, CDCl3, ppm): 7.64 (s,
2H, -pyrrolic-H), 7.54 (d, J = 5 Hz, 1H, Ar-H), 7.37 (d, J = 3.5 Hz, 1H,
Ar-H), 7.160 (t, J = 4 Hz, 1H, Ar-H), 6.95 (d, J = 4 Hz, 2H, -pyrrolic-
H), 6.43 (d, J = 4 Hz, 2H, -pyrrolic-H); 13C NMR (125.7 MHz, CDCl3,
ppm): 143.7, 140.6, 138.1, 131.7, 128.9, 128.7, 126.9, 117.7,
108.4; ESI-MS: C13H11N2S+ [M+H]+: calcd m/z 227.0643, found m/z
227.0562.
General Synthesis of Re(I) Dipyrrinato Complexes
In a 100 mL round bottom flask, Re(CO)5Cl (1 equiv.) and dipyrrin (1
equiv.) were dissolved in dry toluene (1.61 mL) and allowed to
reflux at about 100 °C under inert atmosphere. At 100 °C
triethylamine (2 equiv.) was added and heating continued for 1 h,
then added triphenylphosphine (1 equiv.) and reaction mixture
allowed to heat for another 1 h. Reaction progress was monitored
by TLC, the initial dipyrrin spot vanishes and two new spots
observed. All volatiles were removed under rotary evaporator
10 | J. Name., 2012, 00, 1-3
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