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reaction mixture was filtered and the filtrate was strip-
ped to dryness under reduced pressure. The resulting
white solid was washed with pentane (5 ꢅ 10 mL) and
toluene (5 mL) then dried under vacuum. Yield: 4.00 g
(3.51 mmol), 98% on the basis of the maximum yield
J ¼ 14:2 Hz, 1H, calix-CH2), 4.11 (d, AB, J ¼ 17:6 Hz,
2H, calix-CH2), 3.97 (d, AB, J ¼ 17:6 Hz, 2H, calix-
CH2), 3.66 (d, J ¼ 14:2 Hz, 1H, calix-CH2), 3.51 (d,
J ¼ 14:2 Hz, 1H, calix-CH2), 0.38 (s, 3H, exo-SiCH3),
)1.60 (s, 3H, endo-SiCH3). Anal. Calcd. for C30H26
O4SiTiCl2: C, 60.32; H, 4.39. Found: C, 59.97; H, 4.33.
1
possible under these conditions (3.56 mmol). H NMR
(C6D6) d: 8.61 (m, 4H, arom CH), 7.10–7.20 (m, 8H,
arom CH), 6.99 (s, 4H arom CH ), 6.92 (m, 4H, arom
CH), 6.79 (s, 4H arom CH ), 6.22 (s, 2H, OH), 4.57 (d,
J ¼ 14 Hz, 4H, calix-CH2), 3.10 (d, J ¼ 14 Hz, 1H,
calix-CH2), 2.39 (s, 12H, o-Me C6H4), 1.28 (s, 18H, t-
Bu), 0.93 (s, 18H, t-Bu). 13C NMR (C6D6): 151.4, 146.4,
145.6, 144.6, 142.7, 136.8, 132.5, 132.1, 131.6, 131.3,
129.7, 126.7, 126.4, 125.9, 34.3 (C(CH3)3), 33.2 (calix-
CH2), 33.1 (C(CH3)3), 32.2 (C(CH3)3), 31.5 (C(CH3)3).
MS(EI): Mþ (1138).
3.3.3. (DMSMC)TiCl2 (11)
A pentane (5.0 mL) solution of TiCl4 (0.208 g, 1.09
mmol) was added dropwise into a stirred suspension of
(DMSMC)H2 (0.536 g, 1.00 mmol) in ether (30 mL) at
)40 °C. The mixture turned orange-brown and was
warmed slowly to room temperature and let stir for 12 h.
Volatiles were then removed under vacuum, the residue
was washed with pentane (3 ꢅ 10 mL), and the orange
product was dried in vacuo. Yield: 0.62 g, 95%. 1H
NMR (C6D6) d: 6.88 (d, J ¼ 2 Hz, 2H, arom CH), 6.77
(d, J ¼ 2 Hz, 2H, arom CH), 6.73 (d, J ¼ 2 Hz, 2H,
arom CH), 6.55 (d, J ¼ 2 Hz, 2H, arom CH), 4.54 (d,
J ¼ 14:4 Hz, 1H, calix-CH2), 4.39 (d, J ¼ 14:8 Hz, 1H,
calix-CH2), 3.86 (d, AB, J ¼ 16:8 Hz, 2H, calix-CH2),
3.76 (d, AB, J ¼ 17:6 Hz, 2H, calix-CH2), 3.33 (d,
J ¼ 14:8 Hz, 1H, calix-CH2), 3.24 (d, J ¼ 14:4 Hz, 1H,
calix-CH2), 2.21 (s, 3H, p-Me-calix), 2.00 (s, 3H, p-Me-
calix), 0.29 (s, 3H, exo-SiCH3), -1.38 (s, 3H, endo-
SiCH3). 12C NMR (CDCl3): 163.3, 149.7, 138.4, 134.8,
132.1, 131.3, 131.2, 130.7, 129.7, 129.1, 128.8. 127.0,
39.3 (calix-CH2), 36.2 (calix-CH2), 35.8 (calix-CH2),
21.0 (p-Me-calix), 4.0 (exo-SiCH3), -2.6 (endo-SiCH3).
Anal. Calcd. for C34H34O4SiTiCl2: C, 62.49; H, 5.24.
Found: C, 62.30; H, 5.36.
3.3. Synthesis of titanium complexes 9–12
3.3.1. (DESC)TiCl2 (9)
A pentane (10 mL) solution of TiCl4 (0.544 g, 2.86
mmol) was added dropwise into a stirred suspension of
(DESC)H2 (2.00 g, 2.73 mmol) in ether (50 mL) at )40
°C. The mixture turned orange-brown and was warmed
gradually to room temperature and let stir for 24 h.
Volatiles were then removed under vacuum, the residue
was washed with pentane (3 ꢅ 10 mL), and the orange
product was dried in vacuo. Yield: 2.01 g, 87%. 1H NMR
(CDCl3) d: 7.23 (s, 2H, arom CH), 7.12 (s, 2H, arom
CH), 7.10 (s, 2H, arom CH), 7.04 (s, 2H, arom CH), 4.40
(d, J ¼ 14 Hz, 1H, calix-CH2), 4.38 (d, J ¼ 14:2 Hz, 1H,
calix-CH2), 4.02 (d, AB, J ¼ 16 Hz, 2H, calix-CH2), 3.96
(d, AB, J ¼ 16 Hz, 2H, calix-CH2), 3.60 (d, J ¼ 14:2 Hz,
1H, calix-CH2), 3.47 (d, J ¼ 14 Hz, 1H, calix-CH2), 1.32
(s, 18H, t-Bu), 1.31 (s, 18H, t-Bu), 0.88 (br m, 5H, exo-
SiCH2CH3), 0.29 (t, 3H, endo-SiCH2CH3), -1.40 (q, 2H,
endo-SiCH2CH3). 13C NMR (CDCl3): 162.2, 149.1,
147.9, 144.5, 137.5, 128.6, 128.5, 127.2, 126.9, 126.4,
125.6, 124.9, 39.9 (calix-CH2), 36.6 (calix-CH2), 35.9
(calix-CH2), 34.6 (C(CH3)3), 34.2 (C(CH3)3, 31.7
(C(CH3)3), 31.6 (C(CH3)3), 8.9 (exo-SiCH2CH3), 7.6
(exo-SiCH2CH3), 6.9 (endo-SiCH2CH3), 3.8 (endo-
SiCH2CH3). Anal. Calcd. for C48H62O4SiTiCl2: C,
67.84; H, 7.35. Found: C, 67.64; H, 7.42.
3.3.4. (DPSC)TiCl2 (12)
A pentane (10 mL) solution of TiCl4 (0.458 g, 2.41
mmol) was added dropwise into a stirred suspension of
(DPSC)H2 (2.00 g, 2.41 mmol) in ether (50 mL) at )40
°C. The mixture turned orange-brown and was warmed
slowly to room temperature and let stir for 12 h. Vola-
tiles were then removed under vacuum, the residue was
washed with pentane (3 ꢅ 5 mL), and the orange prod-
1
uct was dried in vacuo. Yield: 1.88 g, 82%. H NMR
(C6D6) d: 7.65 (m, 2H, arom CH), 7.24 (br d, 2H, arom
CH), 6.99-7.13 (m, 8H, arom CH), 6.82 (br d, 2H, arom
CH), 6.66 (br t, 2H, arom CH), 6.27 (d, J ¼ 7 Hz, 2H,
arom CH), 5.16 (d, J ¼ 15:4 Hz, 1H, calix-CH2), 4.93
(d, J ¼ 14:2 Hz, 1H, calix-CH2), 4.17 (d, AB, J ¼ 17:2
Hz, 2H, calix-CH2), 3.81 (d, AB, J ¼ 17:2 Hz, 2H, calix-
CH2), 3.38 (d, J ¼ 15:4 Hz, 1H, calix-CH2), 3.12 (d,
J ¼ 15:0 Hz, 1H, calix-CH2), 1.40 (s, 18H, t-Bu), 1.16 (s,
18H, t-Bu). 12C NMR (C6D6): 163.3, 150.4, 147.2, 145.3,
138.9, 138.4, 135.4, 133.6, 133.5, 130.6, 130.5, 129.4,
129.3, 129.1. 128.2, 125.6, 125.2, 40.1 (calix-CH2), 38.7
(calix-CH2), 38.4 (calix-CH2), 34.5 (C(CH3)3), 34.4
(C(CH3)3), 32.0 (s, C(CH3)3), 31.6 (s, C(CH3)3). Anal.
Calcd. for C56H62O4SiTiCl2: C, 71.10; H, 6.60. Found:
C, 70.98; H, 6.41.
3.3.2. (DMSHC)TiCl2 (10)
A pentane (8.0 mL) solution of TiCl4 (0.379 g, 2.00
mmol) was added dropwise into a stirred suspension of
(DMSHC)H2 (0.805 g, 1.67 mmol) in ether (50 mL) at
)50 °C. The mixture turned orange-brown and was
warmed gradually to room temperature and let stir for
24 h. The precipitate was filtered, washed with pentane
(3 ꢅ 7 mL), and the orange product was dried in vacuo.
Yield: 0.838 g, 84% based on the amount of
1
(DMSHC)H2. H NMR (CDCl3) d: 6.84-7.24 (m, 12H,
arom CH), 4.40 (d, J ¼ 14:8 Hz, 1H, calix-CH2), 4.34 (d,