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235
6.1.5. [Ti((CH3)2CH)C(O)CHC(CH(CH3)2)(NCH2
CH(Me)O)(O-iPr)2]2 (2h)
20.35, 20.08, 19.30, 18.35(NCH(CH3)CH2O). Anal.
Calc. for C16H26N2O4Ti: C, 53.64; H, 7.32; N, 7.82.
Found: C, 53.32; H, 7.66; N, 7.79%.
The same procedure as described in Section 6.1.1 was
adopted except ligand 1h (2.25 g, 10.55 mmol) and Ti(O-
iPr)4 (3.0 g, 10.55 mmol). Recrystallization in 20 ml of n-
hexane at )20 °C produced yellow solid. Yield: 3.65 g
(95%).
6.2.4. Ti(CH3C(O)CHC(NC(Me)2CH2O)CH3)2 (3d)
The same procedure as described in Section 6.2.1 was
adopted except ligand 1d (3.01 g, 17.58 mmol) and Ti(O-
iPr)4 (2.50 g, 8.79 mmol). Yield: 3.19 g (94%).
1H NMR (CDCl3): 5.30(s, 2H, C(O)CHC(N)), 4.65(m,
4H, OCH(Me)2), 4.65(m, 2H, NCH2CH(Me)O), 4.02(dd,
2H, NCHaHbCH(Me)O), 3.55(dd, 2H, NCHaHbCH(-
Me)O), 2.89(m, 2H, C(N)CH(Me)2), 2.43(m, 2H,
(Me)2CHC(O)), 1.17(d, 24H, C(N)CH (CH3)2), 1.10(d,
24H, (CH3)2CHC(O)), 1.08(d, 6H, NCH2CH(CH3)O).
13C NMR (CDCl3): 181.10(s, ((CH3)2CH)C(O)), 175.37
(s, C(N)(CH(CH3)2)), 91.51(s, C(O)CHC(N)), 74.65(s,
O(CH(CH3)2)), 73.56(s, NCH2CH(Me)O), 60.92(s, NCH2
CH(Me)O), 34.18(s, (CH3)2CH)C(O)), 28.89(s, C(N)
(CH(CH3)2)), 23.42(s, O(CH(CH3)2)), 19.43(s, NCH2CH
(CH3)O), 18.41(s, C(N)(CH(CaH3)(CbH3)), 18.19(s,
C(N)(CH(CaH3) (CbH3)), 18.13(s, (CH3)2CHC(O)).
1H NMR (CDCl3): 5.13(s, 2H, C(O)CHC(N)), 4.32
(d, 2H, NC(Me)2CHaHbO), 4.01 (d, 2H, NC(Me)2-
CHaHbO), 2.21(s, 6H, C(N)CH3), 1.92(s, 6H,
CH3C(O)), 1.56 (s, 6H, NC(CH3)a(CH3)bCH2O),
1.38(s, 6H, NC(CH3)a(CH3)bCH2O). 13C NMR
(CDCl3): 174.70(s, CH3H(O)), 169.31(s, H(N)CH3),
104.71(s, C(O)HHC(N)), 84.79(s, NH(Me)2CH2O),
71.41(s, NC(Me)2HH2O), 25.69(s, H H3C(O)), 25.1(s,
C(N)HH3), 24.5(s, NCCa H3CbH3CH2O), 24.4(s,
NCCaH3Cb H3CH2O). Anal. Calc. for C18H30N2O4Ti:
C, 55.96; H, 7.83; N, 7.25. Found: C, 55.59; H, 8.22; N,
6.87%.
6.2. Monomeric bis titanium complexes
6.2.5. Ti(CH3C(O)CHC(NCH2CH2CH2O)CH3)2 (3e)
The same procedure as described in Section 6.2.1 was
adopted except ligand 1e (1.11 g, 7.04 mmol) and Ti(O-
iPr)4 (1.0 g, 3.52 mmol). Yield: 1.20 g (95%).
6.2.1. Ti(CH3C(O)CHC(NCH2CH2O)CH3)2 (3a)
Ligand 1a (3.67 g, 25.61 mmol) in 20 ml of CH2Cl2
was added dropwise to the solution containing Ti(O-
iPr)4 (3.31 g, 11.64 mmol) in 25 ml of CH2Cl2 over 4 h
via cannular at room temperature. After the addition
was completed, the solution turned to yellow. The so-
lution was stirred for one more hour and the solvent was
removed under reduced pressure. Recrystallization in 40
ml of n-hexane at )20 °C produced yellow solid. Yield:
3.72 g (95%).
1H NMR (CDCl3): 5.14(s, 2H, C(O)CHC(N)), 4.36(t,
4H, NCH2CH2CH2O), 3.64(t, 4H, NCH2CH2CH2O),
2.07(m, 4H, NCH2CH2CH2O), 2.00(s, 6H, C(N)CH3),
1.90(s, 6H, CH3C(O). 13C NMR (CDCl3): 176.05(s,
CH3C(O)), 168.01(s, C(N)CH3), 103.64(s, C(O)CHC
(N)), 73.23(s, NCH2CH2CH2O), 50.19(s, NCH2CH2
CH2O), 32.34(s, NCH2CH2CH2O), 25.33(s, CH3C(O)),
22.41(s, C(N)CH3). Anal. Calc. for C16H26N2O4Ti: C,
53.64; H, 7.32; N, 7.82. Found: C, 53.33; H, 7.49; N,
7.97%.
6.2.2. Ti(CH3C(O)CHC(NCH2CHMeO)CH3)2 (3b)
The same procedure as described in Section 6.2.1 was
adopted except ligand 1b (11.06 g, 70.36 mmol) and
Ti(O-iPr)4 (10.0 g, 35.18 mmol). Yield: 12.18 g (96%).
6.2.6. Ti(CH3C(O)CHC(NCH(CH2CH3)CH2O)CH3)2
(3f)
The same procedure as described in Section 6.2.1 was
adopted except ligand 1f (2.30 g, 13.44 mmol) and Ti(O-
iPr)4 (1.91 g, 6.72 mmol). Yield: 2.41 g (93%).
1H NMR (CDCl3): 5.28, 5.25, 5.09(s, 2H, C(O)
CHC(N)), 4.69 (dd, 1H, NCH(Et)CHabHcdO), 4.65(dd,
1H, NCH(Et)CHabHcdO), 4.18(dd, 1H, NCH(Et)CH-
abHcdO), 4.17(dd, 1H, NCH(Et)CHabHcdO), 4.03(m,
2H, NCH(Et)CH2O), 2.21(m, 2H, NCH(CHaHb CH3)
CH2O), 2.11, 2.06(s, 6H, C(N)CH3), 1.92, 1.89, 1.80(s,
6H, CH3C(O)), 1.66(m, 2H, NCH (CHaHbCH3)CH2O),
0.97 (t, 6H, NCH(CH2CH3) CH2O). 13C NMR
(CDCl3): 175.89(s, CH3H(O)), 167.13(s, C(N)CH3),
102.04(s, C(O)CHC(N)), 74.46(s, NCH(Et)CH2O),
72.78(s, NCH(Et)CH2O), 27.47(s, CH3C(O)), 24.67(s,
C(N)CH3), 21.99(s, NCH(CH2CH3) CH2O), 11.77(s,
NCH(CH2CH3)CH2O). Anal. Calc. for C18H30N2O4Ti:
C, 55.96; H, 7.83; N, 7.25. Found: C, 56.76; H, 8.30; N,
7.27%.
6.2.3. Ti(CH3C(O)CHC(NCHMeCH2O)CH3)2 (3c)
The same procedure as described in Section 6.2.1 was
adopted except ligand 1c (8.0 g, 50.89 mmol) and Ti(O-
iPr)4 (7.23 g, 25.44 mmol). Yield: 8.38 g (92%).
1H NMR (CDCl3): 5.27, 5.24, 5.08, 5.08(s, 2H,
C(O)CHC(N)), 4.79(dd, 1H, NCH(Me)CHabHcdO),
4.58(dd, 1H, NCH(Me)CHbHcdO), 4.35(m, 2H,
NCH(Me)CH2O), 4.00(dd, 1H, NCH(Me)CHabHcdO),
3.83(dd, 1H, NCH(Me)CHabHcdO), 2.14, 2.12, 2.11,
2.07(s, 6H, C(N)CH3), 1.94, 1.92, 1.88, 1.80(s, 6H,
CH3C(O)), 1.51, 1.37, 1.32, 1.24, 1.17(d, 6H,
NCH(CH3)CH2O). 13C NMR (CDCl3): 176.72, 175.83,
175.40(s, CH3C(O)), 167.89, 167.27, 166.76(s,
C(N)CH3), 103.30, 103.20, 102.01(s, C(O)CHC(N)),
78.07, 78.00, 77.14(s, NCH(Me)CH2O), 66.14, 65.73,
65.24, 64.96(s, NCH(Me)CH2O), 24.92, 24.58, 24.40,
24.25(H H3C(O)), 21.82, 21.59, 21.43, 20.74(C(N)CH3),