G. Romanowski / Journal of Molecular Catalysis A: Chemical 368–369 (2013) 137–144
139
3J = 8 Hz) (aromatic); 4.91 (1H, m) (methine); 4.30 (1H, dd, 3J = 8 Hz,
4J = 6 Hz), 4.06 (1H, dd, 3J = 8 Hz, 4J = 3 Hz) (methylene); 1.51 (3H, d,
3J = 8 Hz) (methyl). 51V NMR (CD3OD, ppm) major (60%): −539.9,
minor (40%): −538.1.
2.3.3. ꢀ-Oxido-bis({R(−)-2-[(2-oxidopropyl)iminomethyl]-4-
methoxyphenolato-ꢁ3N,O,O’}oxidovanadium(V))
(3)
Yield 75%. Anal. Calc. for C22H26N2O9V2: C, 46.8; H, 4.6; N,
5.0. Found: C, 46.9; H, 4.7; N, 5.1. IR (KBr, cm−1): 1632 (ꢂC N);
972 (ꢂV ). UV–Vis spectrum in MeOH [ꢃmax (nm), ε (M−1 cm−1)]:
2.3.7. ꢀ-Oxido-bis({R(−)-2-[(2-oxidopropyl)iminomethyl]-4-
nitrophenolato-ꢁ3N,O,O’}oxidovanadium(V))
O
284 (9680), 351 (4230). CD spectrum in MeOH [ꢃmax (nm), ꢄε
(M−1 cm−1)]: 254 (−3.37), 284 (2.65), 355 (−5.94). 1H NMR (CD3OD,
ppm) major (60%): 8.68 (1H, s) (azomethine); 7.19 (2H, m), 6.93
(1H, t, 3J = 8 Hz) (aromatic); 5.21 (1H, m) (methine); 4.45 (1H, dd,
3J = 8 Hz, 4J = 3 Hz), 3.69 (1H, dd, 3J = 8 Hz, 4J = 6 Hz) (methylene);
1.36 (3H, d, 3J = 8 Hz) (methyl); 3.90 (3H, s) (methoxy); minor
(40%): 8.66 (1H, s) (azomethine); 7.20 (2H, ov), 6.94 (1H, ov) (aro-
matic); 5.00 (1H, m) (methine); 4.32 (1H, dd, 3J = 8 Hz, 4J = 6 Hz),
4.13 (1H, dd, 3J = 8 Hz, 4J = 3 Hz) (methylene); 1.45 (3H, d, 3J = 8 Hz)
(methyl); 3.85 (3H, s) (methoxy). 51V NMR (CD3OD, ppm) major
(60%): −537.7, minor (40%): −534.2.
(7)
Yield 74%. Anal. Calc. for C20H20N4O11V2: C, 40.4; H, 3.4; N, 9.4.
Found: C, 40.3; H, 3.6; N, 9.3. IR (KBr, cm−1): 1643 (ꢂC N); 975 (ꢂV O).
UV–Vis spectrum in MeOH [ꢃmax (nm), ε (M−1 cm−1)]: 347 (14,840).
CD spectrum in MeOH [ꢃmax (nm), ꢄε (M−1 cm−1)]: 255 (−4.23),
314 (4.33), 359 (−7.02). 1H NMR (CD3OD, ppm) major (60%): 8.72
(1H, s) (azomethine); 8.49 (1H, d, 4J = 3 Hz), 8.29 (1H, dd, 3J = 8 Hz,
4J = 3 Hz), 6.99 (1H, d, 3J = 8 Hz) (aromatic); 5.41 (1H, m) (methine);
4.42 (1H, dd, 3J = 8 Hz, 4J = 3 Hz), 3.75 (1H, dd, 3J = 8 Hz, 4J = 6 Hz)
(methylene); 1.37 (3H, d, 3J = 8 Hz) (methyl); minor (40%): 8.73
(1H, ov) (azomethine); 8.48 (1H, ov), 8.27 (1H, ov), 7.05 (1H, d,
3J = 8 Hz) (aromatic); 4.95 (1H, m) (methine); 4.25 (1H, dd, 3J = 8 Hz,
4J = 6 Hz), 4.02 (1H, dd, 3J = 8 Hz, 4J = 3 Hz) (methylene); 1.45 (3H, d,
3J = 8 Hz) (methyl). 51V NMR (CD3OD, ppm) major (60%): −536.7,
minor (40%): −539.7.
2.3.4. ꢀ-Oxido-bis({R(−)-2-[(2-oxidopropyl)iminomethyl]-3,5-
dimethoxyphenolato-ꢁ3N,O,O’}oxidovanadium(V))
(4)
Yield 77%. Anal. Calc. for C24H30N2O11V2: C, 46.2; H, 4.8; N, 4.5.
Found: C, 46.0; H, 4.8; N, 4.4. IR (KBr, cm−1): 1602 (ꢂC N); 973 (ꢂV O).
UV–Vis spectrum in MeOH [ꢃmax (nm), ε (M−1 cm−1)]: 317 (17,660).
CD spectrum in MeOH [ꢃmax (nm), ꢄε (M−1 cm−1)]: 252 (−2.86),
285 (2.52), 350 (−4.22). 1H NMR (CD3OD, ppm) major (60%): 8.87
(1H, s) (azomethine); 6.23 (1H, d, 4J = 3 Hz), 6.17 (1H, d, 4J = 3 Hz)
(aromatic); 5.17 (1H, m) (methine); 4.42 (1H, dd, 3J = 8 Hz, 4J = 3 Hz),
3.66 (1H, dd, 3J = 8 Hz, 4J = 6 Hz) (methylene); 1.34 (3H, d, 3J = 8 Hz)
(methyl); 3.89 (3H, s), 3.85 (3H, s) (methoxy); minor (40%): 8.85
(1H, s) (azomethine); 6.19 (1H, ov), 6.15 (1H, ov) (aromatic); 4.96
(1H, m) (methine); 4.30 (1H, dd, 3J = 8 Hz, 4J = 6 Hz), 4.06 (1H, dd,
3J = 8 Hz, 4J = 3 Hz) (methylene); 1.42 (3H, d, 3J = 8 Hz) (methyl); 3.90
(3H, ov), 3.86 (3H, ov) (methoxy). 51V NMR (CD3OD, ppm) major
(60%): −538.3, minor (40%): −536.2.
2.3.8. ꢀ-Oxido-bis({R(−)-2-[(2-oxidopropyl)iminomethyl]-5-
hydroxyphenolato-ꢁ3N,O,O’}oxidovanadium(V))
(8)
Yield 80%. Anal. Calc. for C20H22N2O9V2: C, 44.8; H, 4.1; N, 5.2.
Found: C, 44.7; H, 4.2; N, 5.1. IR (KBr, cm−1): 1599 (ꢂC N); 961 (ꢂV O).
UV–Vis spectrum in MeOH [ꢃmax (nm), ε (M−1 cm−1)]: 288 (9910),
350 (4620). CD spectrum in MeOH [ꢃmax (nm), ꢄε (M−1 cm−1)]:
253 (−3.44), 282 (3.39), 351 (−5.40). 1H NMR (CD3OD, ppm) major
(60%): 8.58 (1H, s) (azomethine); 7.41 (1H, t, 3J = 8 Hz), 6.47 (1H, t,
3J = 8 Hz), 6.35 (1H, dd, 3J = 8 Hz, 4J = 3 Hz) (aromatic); 5.30 (1H, m)
(methine); 4.40 (1H, dd, 3J = 8 Hz, 4J = 3 Hz), 3.66 (1H, dd, 3J = 8 Hz,
4J = 6 Hz) (methylene); 1.39 (3H, d, 3J = 8 Hz) (methyl); minor (40%):
8.59 (1H, ov) (azomethine); 7.42 (1H, ov), 6.46 (1H, ov), 6.34 (1H,
ov) (aromatic); 5.10 (1H, m) (methine); 4.28 (1H, dd, 3J = 8 Hz,
4J = 6 Hz), 4.05 (1H, dd, 3J = 8 Hz, 4J = 3 Hz) (methylene); 1.46 (3H,
d, 3J = 8 Hz) (methyl). 51V NMR (CD3OD, ppm) major (60%): −536.1,
minor (40%): −538.9.
2.3.5. ꢀ-Oxido-bis({R(−)-2-[(2-oxidopropyl)iminomethyl]-4-
methylphenolato-ꢁ3N,O,O’}oxidovanadium(V))
(5)
Yield 79%. Anal. Calc. for C22H26N2O7V2: C, 49.6; H, 4.9; N, 5.3.
Found: C, 49.5; H, 4.8; N, 5.5. IR (KBr, cm−1): 1636 (ꢂC N); 970 (ꢂV O).
UV–Vis spectrum in MeOH [ꢃmax (nm), ε (M−1 cm−1)]: 278 (9830),
327 (4370). CD spectrum in MeOH [ꢃmax (nm), ꢄε (M−1 cm−1)]:
254 (−4.12), 299 (3.31), 360 (−10.28). 1H NMR (CD3OD, ppm) major
(60%): 8.62 (1H, s) (azomethine); 7.31 (2H, m) 6.84 (1H, d, 3J = 8 Hz)
(aromatic); 5.20 (1H, m) (methine); 4.47 (1H, dd, 3J = 8 Hz, 4J = 3 Hz),
3.66 (1H, dd, 3J = 8 Hz, 4J = 6 Hz) (methylene); 2.32 (1H, s), 1.33 (3H,
d, 3J = 8 Hz) (methyl); minor (40%): 8.64 (1H, s) (azomethine); 7.33
(2H, ov), 6.86 (1H, ov) (aromatic); 4.96 (1H, m) (methine); 4.36 (1H,
dd, 3J = 8 Hz, 4J = 6 Hz), 4.08 (1H, dd, 3J = 8 Hz, 4J = 3 Hz) (methylene);
2.33 (1H, ov), 1.45 (3H, d, 3J = 8 Hz) (methyl). 51V NMR (CD3OD,
ppm) major (60%): −537.9, minor (40%): −533.8.
2.3.9. ꢀ-Oxido-bis({R(−)-2-[(2-oxidopropyl)iminomethyl]-6-
tert-butylphenolato-ꢁ3N,O,O’}oxidovanadium(V))
(9)
Yield 77%. Anal. Calc. for C28H38N2O7V2: C, 54.6; H, 6.2; N, 4.5.
Found: C, 54.7; H, 6.3; N, 4.4. IR (KBr, cm−1): 1635 (ꢂC N); 975 (ꢂV O).
UV–Vis spectrum in MeOH [ꢃmax (nm), ε (M−1 cm−1)]: 277 (9680),
328 (4120). CD spectrum in MeOH [ꢃmax (nm), ꢄε (M−1 cm−1)]:
256 (−2.65), 295 (2.33), 359 (−6.41). 1H NMR (CD3OD, ppm) major
(60%): 8.76 (1H, s) (azomethine); 7.47 (1H, d, 3J = 8 Hz), 7.32 (1H, d,
3J = 8 Hz), 6.80 (1H, t, 3J = 8 Hz) (aromatic); 5.27 (1H, m) (methine);
4.38 (1H, dd, 3J = 8 Hz, 4J = 3 Hz), 3.64 (1H, dd, 3J = 8 Hz, 4J = 6 Hz)
(methylene); 1.38 (3H, d, 3J = 8 Hz) (methyl); 1.49 (9H, s) (tert-
butyl); minor (40%): 8.78 (1H, s) (azomethine); 7.48 (1H, ov), 7.33
(1H, ov), 6.84 (1H, t, 3J = 8 Hz) (aromatic); 5.01 (1H, m) (methine);
4.26 (1H, dd, 3J = 8 Hz, 4J = 6 Hz), 4.03 (1H, dd, 3J = 8 Hz, 4J = 3 Hz)
(methylene); 1.46 (3H, d, 3J = 8 Hz) (methyl); 1.48 (9H, ov) (tert-
butyl). 51V NMR (CD3OD, ppm) major (60%): −550.4, minor (40%):
−553.6.
2.3.6. ꢀ-Oxido-bis({R(−)-2-[(2-oxidopropyl)iminomethyl]-4-
bromophenolato-ꢁ3N,O,O’}oxidovanadium(V))
(6)
Yield 81%. Anal. Calc. for Br2C20H20N2O7V2: C, 36.3; H, 3.0; N, 4.2.
Found: C, 36.4; H, 3.2; N, 4.2. IR (KBr, cm−1): 1634 (ꢂC N); 974 (ꢂV O).
UV–Vis spectrum in MeOH [ꢃmax (nm), ε (M−1 cm−1)]: 282 (10,040),
330 (4940). CD spectrum in MeOH [ꢃmax (nm), ꢄε (M−1 cm−1)]:
253 (−3.91), 285 (2.28), 361 (−6.32). 1H NMR (CD3OD, ppm) major
(60%): 8.73 (1H, s) (azomethine); 7.66 (1H, d, 4J = 3 Hz), 7.56 (1H, dd,
3J = 8 Hz, 4J = 3 Hz), 6.87 (1H, d, 3J = 8 Hz) (aromatic); 5.24 (1H, m)
(methine); 4.39 (1H, dd, 3J = 8 Hz, 4J = 3 Hz), 3.62 (1H, dd, 3J = 8 Hz,
4J = 6 Hz) (methylene); 1.39 (3H, d, 3J = 8 Hz) (methyl); minor (40%):
8.74 (1H, ov) (azomethine); 7.64 (1H, ov), 7.54 (1H, ov), 6.92 (1H, d,
2.3.10.
ꢀ-Oxido-bis({R(−)-2-[(2-oxidopropyl)iminomethyl]naphtholato-
ꢁ3N,O,O’}oxidovanadium(V)
(10)
Yield 74%. Anal. Calc. for C28H26N2O7V2: C, 55.6; H, 4.3; N, 4.6.
Found: C, 55.5; H, 4.4; N, 4.7. IR (KBr, cm−1): 1622 (ꢂC N); 978 (ꢂV O).