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S.H. Kim et al. / Journal of Organometallic Chemistry 694 (2009) 3409–3417
EI-MS (% intensity): m/z calc.: 440 (22.73%, M+), 220 (100.00%,
3.9. Synthesis of N,N0-dibenzyl-N,N0-bis[(3-methoxy-5-methyl-
[CH2NMe{CH2(3-methyl-5-tert-butyl-2-hydroxyphenyl)}]+), 177
(78.42%, [CH2(3-methyl-5-tert-butyl-2-hydroxyphenyl)]+).
HRMS (EI) m/z Calc. 440.3403. Found: 440.3398.
2hydroxyphenyl)methylene]-1,2-diaminoethane (Lig8H2)
The desired product Lig8H2 was prepared from N,N0-dibenzyle-
thylenediamine (2.51 g, 10.4 mmol), 2-methoxy-4-methylphenol
(2.88 g, 20.9 mmol) and 37% aqueous formaldehyde (1.69 g,
20.9 mmol) in a yield of 86.2% (4.85 g) in a manner analogous to
the procedure for Lig2H2.
3.6. Synthesis of N,N0-dibenzyl-N,N0-bis[(3-methyl-5-tert-butyl-2-
hydroxyphenyl)methyl-ene]-1,2-diaminoethane (Lig4H2)
The desired product Lig4H2 was prepared from N,N0-dibenzyle-
thylenediamine (8.83 g, 36.7 mmol), 2-methyl-4-tert-butylphenol
(12.1 g, 73.5 mmol) and 37% aqueous formaldehyde (5.96 g,
73.5 mmol) in a yield of 84.5% (18.4 g) in a manner analogous to
the procedure for Lig2H2.
1H NMR (CDCl3, 400.15 MHz, ppm): d 10.52 (s, 2H, OH), 7.26–
7.12 (m, 10H, Ph-H), 6.61 (s, 2H, aryl-H), 6.34 (s, 2H, aryl-H), 3.85
(s, 6H, OMe), 3.62 (s, 4H, aryl-CH2N), 3.52 (s, 4H, PhCH2N), 2.68
(s, 4H, NCH2CH2N), 2.24 (s, 6H, aryl-CH3).
13C{1H} NMR (CDCl3, 100.63 MHz, ppm): d 147.52, 144.15,
136.28, 129.36, 128.55, 128.21, 127.59, 121.41, 120.90, 111.87
(aryl-C and Ph-C), 58.63 (phenyl-CH2N), 57.87 (OMe), 55.77 (aryl-
CH2N), 50.09 (NCH2CH2N), 20.99 (aryl-CH3).
1H NMR (CDCl3, 400.15 MHz, ppm): d 10.48 (s, 2H, OH), 7.26–
7.12 (m, 10H, Ph-H), 7.04 (s, 2H, aryl-H), 6.78 (s, 2H, aryl-H), 3.66
(s, 4H, aryl-CH2N), 3.52 (s, 4H, PhCH2N), 2.69 (s, 4H, NCH2CH2N),
2.21 (s, 6H, aryl-CH3), 1.25 (s, 18H, aryl-CMe3).
EI-MS (% intensity): m/z calc.: 540 (100.00%, M+), 270 (71.09%,
[CH2NCH2Ph{CH2(3-methoxy-5-methyl-2-hydroxyphenyl)}]+),
373 (55.42%, M+ꢀ[CH2(3,5-dimethyl-2-hydroxyphenyl)]), 151
13C{1H} NMR (CDCl3, 100.63 MHz, ppm): d 153.06, 141.43,
136.28, 129.44, 128.52, 127.61, 126.99, 124.06, 123.09, 120.05
(aryl-C and Ph-C), 58.63 (aryl-CH2N), 58.30 (PhCH2N), 49.98
(NCH2CH2N), 33.85 (aryl-CMe3), 31.60 (aryl-CMe3), 16.06 (aryl-CH3).
EI-MS (% intensity): m/z calc.: 592 (100.00%, M+), 501 (16.37%,
M+ꢀCH2Ph), 415 (20.42%, M+ꢀCH2(3-methyl-5-tert-butyl-2-
hydroxyphenyl)), 296 (65.54%, CH2NCH2Ph{CH2(3-methyl-5-t-bu-
tyl-2-hydroxyphenyl)}+), 177 (66.74%, [CH2(3-methyl-5-tert-bu-
tyl-2-hydroxyphenyl)]+), 91 (87.17%, [CH2Ph]+).
(69.43%,
[CH2(3-methoxy-5-methyl-2-hydroxyphenyl)]+),
91
(100.00%, [CH2Ph]+), 77 (60.14%, [Ph]+).
HRMS (EI) m/z Calc. 540.2988. Found: 540.2983.
3.10. Synthesis of Lig2Ti(O-i-Pr)2 (2)
To a stirred colorless solution of Lig2H2 (0.76 g, 1.5 mmol) in
30 mL toluene was added dropwise at room temperature a solution
of Ti(O-i-Pr)4 (0.44 g, 1.5 mmol) in 20 mL toluene. The reaction
mixture was allowed to warm to room temperature and stirred
for overnight. The residue, obtained by removing the solvent under
vacuum, was recrystallized in hexane. The desired product 2 was
isolated as yellow crystals after the solution remained at ꢀ15 °C
in a refrigerator for a few days (0.90 g, 89.4%).
HRMS (EI) m/z Calc. 592.4029. Found: 529.4025.
3.7. Synthesis of N,N0-dibenzyl-N,N0-bis[(3,5-di-t-butyl-2-
hydroxyphenyl)methylene]-1,2-diaminoethane (Lig6H2)
The desired product Lig6H2 was prepared from N,N0-dibenzyle-
thylenediamine (0.75 g, 3.13 mmol), 2,4-di-tert-butylphenol
(1.29 g, 6.27 mmol) and 37% aqueous formaldehyde (0.512 g,
6.27 mmol) in a yield of 90.1% (1.91 g) in a manner analogous to
the procedure for Lig2H2.
1H NMR (CDCl3, 300.13 MHz, ppm): d 7.30–7.06 (m, 10H, Ph-H),
6.84 (s, 2H, aryl-H), 6.48 (s, 2H, aryl-H), 5.25–5.17 (m, 2H,
OCHMe2), 4.45 (d, 2H, J = 13 Hz, aryl-CH2N), 4.15 (s, 4H, PhCH2N),
3.34 (d, 2H, J = 13.08 Hz, aryl-CH2N), 2.67 (d, 2H, J = 10.27 Hz,
NCH2CH2N), 2.40 (d, 2H, J = 10.35 Hz, NCH2CH2N), 2.21 (s, 6H,
aryl-CH3), 2.15 (s, 6H, aryl-CH3), 1.33 (d, 6H, J = 6.08 Hz, OCHMe2),
1.28 (d, 6H, J = 6.13 Hz, OCHMe2).
1H NMR (CDCl3, 400.15 MHz, ppm): d 10.60 (s, 2H, OH), 7.31–
7.20 (m, 10H, Ph-H), 7.18 (s, 2H, aryl-H), 6.84 (s, 2H, aryl-H), 3.70
(s, 4H, aryl-CH2N), 3.54 (s, 4H, PhCH2N), 2.72(s, 4H, NCH2CH2N),
1.46 (s, 18H, aryl-CMe3), 1.31 (s, 18H, aryl-CMe3).
13C{1H} NMR (CDCl3, 100.63 MHz, ppm): d 153.77, 140.64,
136.54, 135.62, 129.54, 128.46, 127.5, 123.63, 122.98, 121.01
(aryl-C and Ph-C), 59.15 (aryl-CH2N), 58.04 (Ph-CH2N), 49.97
(NCH2CH2N), 34.86 (aryl-CMe3), 34.13 (aryl-CMe3), 31.69 (aryl-
CMe3), 29.60 (aryl-CMe3).
13C{1H} NMR (CDCl3, 300.13 MHz, ppm): d 151.63, 147.74,
133.46, 132.35, 128.00, 127.79, 126.25, 125.26, 122.43, 114.25
(aryl-C and Ph-C), 78.02 (OCHMe2) 59.63 (aryl-CH2N), 57.79
(PhCH2N), 56.5 (NCH2CH2N), 25.99 (OCHMe2), 25.71 (OCHMe2),
20.97 (aryl-CH3), 20.75 (aryl-CH3).
HRMS (EI) m/z Calc. 676.4968. Found: 676.4965.
Elemental Anal. Calc. for C40H52N2O4Ti: C, 71.42; H, 7.79; N,
4.16. Found: C, 71.55; H, 8.03; N, 4.25%.
3.8. Synthesis of N,N0-dimethyl-N,N0-bis[(3-methoxy-5-methyl-2-
hydroxyphenyl)methylene]-1,2-diaminoethane (Lig7H2)
3.11. Synthesis of Lig3Ti(O-i-Pr)2 (3)
The desired product Lig7H2 was prepared from N,N0-dimethyl-
ethylenediamine (0.882 g, 10.0 mmol), 2-methoxy-4-methylphe-
nol (2.76 g, 20.0 mmol) and 37% aqueous formaldehyde (1.62 g,
20.0 mmol) in a yield of 87.3% (3.39 g) in a manner analogous to
the procedure for Lig2H2.
The desired product 3 as yellow crystals in an isolated yield of
89.1% (0.81 g) in a manner analogous to the procedure for 1 using
Lig3H2 (0.66 g, 1.5 mmol) and Ti(O-i-Pr)4 (0.44 g, 1.5 mmol).
1H NMR (CDCl3, 400.15 MHz, ppm): d 7.07 (s, 2H, aryl-H), 6.78
(s, 2H, aryl-H), 5.26–5.20 (m, 2H, OCHMe2), 4.76 (d, 2H,
J = 13.28 Hz, aryl-CH2N), 3.12 (d, 2H, J = 13.36 Hz, aryl-CH2N),
3.08 (d, 2H, J = 9.16 Hz, NCH2CH2N), 2.43 (s, 6H, NMe), 2.27 (s,
6H, aryl-CH3), 1.77 (d, 2H, J = 9.24 Hz, NCH2CH2N), 1.31 (d, 6H,
J = 6.04 Hz, OCHMe2), 1.27 (s, 18H, aryl-CMe3), 1.20 (d, 6H,
J = 6.2 Hz, OCHMe2).
1H NMR (CDCl3, 400.15 MHz, ppm): d 10.61 (s, 2H, OH), 6.59 (s,
2H, aryl-H), 6.36 (s, 2H, aryl-H), 3.82 (s, 6H, OMe), 3.62 (s, 4H, aryl-
CH2N), 2.66 (s, 4H, NCH2CH2N), 2.27 (s, 6H, NMe), 2.22 (s, 6H, aryl-
CH3).
13C{1H} NMR (CDCl3, 100.63 MHz, ppm): d 147.52, 144.40,
128.07, 121.35, 120.76, 111.93 (aryl-C), 61.38 (aryl-CH2N), 55.79
(OMe), 54.48 (NCH2CH2N), 41.94 (NMe), 20.95 (aryl-CH3).
EI-MS (% intensity): m/z calc.: 388 (25.43%, M+), 151 (100.00%,
[CH2(3-methoxy-5-methyl-2-hydroxyphenyl)]+), 137 (17.00%, (3-
methoxy-5-methyl-2-hydroxy-phenyl)]+).
13C{1H} NMR (CDCl3, 100.63 MHz, ppm): d 153.91, 139.48,
126.97, 124.05, 123.86, 123.16 (aryl-C), 77.09, 77.05 (OCHMe2),
65.07 (aryl-CH2N), 51.43 (NCH2CH2N), 47.06 (NMe), 33.79
(aryl-CMe3), 31.71 (aryl-CMe3), 26.23 (OCHMe2), 25.90 (OCHMe2),
17.64 (aryl-CH3).
HRMS (EI) m/z Calc. 388.2362. Found: 388.2364.