S. O. Baumann, U. Schubert et al.
FULL PAPER
1H and 13C solution NMR spectra were recorded on a Bruker AV-
microcrystalline solid precipitated upon evaporation of the solvent
in vacuo which was re-dissolved by addition of 0.20 mL of di-
ANCE 250 (250.13 MHz {1H}, 62.86 MHz {13C}) and a Bruker
DPX 300 spectrometer (300.13 MHz {1H}, 75.47 MHz {13C}) chloromethane. Colorless crystals were obtained from the yellow
equipped with a 5 mm inverse-broadband probe head and a z-gra-
dient unit. 2D NMR spectra were measured with Bruker standard
pulse programs COSY (Correlation Spectroscopy), TOCSY (Total
Correlation Spectroscopy), HSQC (Heteronuclear Single Quantum
Correlation), and HMBC (Heteronuclear Multiple-Bond Corre-
lation). A numbering scheme for the carbon atoms of the oximate
ligands is given in Figure 11.
solution after one day of storing the reaction mixture at 2 °C. The
crystals were washed with several portions of pentane at –20 °C
and dried in vacuo; yield 968 mg (94%). 1H NMR (CDCl3, 20 °C):
δ = 4.55/4.46 (q, J = 6.2 Hz, 1 H, CHMe2), 2.44/2.29 (q, J = 7.6 Hz,
2 H, CH2Me), 1.99/1.96 (s, 3 H, CCH3), 1.18/1.16 [s, 3 H, CH-
(CH3)2], 1.06/1.02 [d, J = 6.2 Hz, 6 H, CH(CH3)2] ppm. 13C{1H}
NMR (CDCl3, 20 °C): δ = 152 (C=N), 77.2/76.3 (CHMe2), 29.1
(CH2Me), 26.4/25.7 (CHMe2), 17.1 (CCH3), 9.7 (CH2CH3) ppm.
IR (CH Cl ): ν = 2873 (s), 2880 (s), 1648 (m), 1461 (m), 1438 (w),
˜
2
2
1376 (m), 1161 (m), 1128 (vs), 1074 (w), 1003 (s), 947 (m), 851 (sh),
813 (w), 627 (s), 562 (s), 508 (w) cm–1.
Synthesis of [Ti(OiPr)3(ON=C6H10)]2·[Ti(OiPr)2(ON=C6H10)2]2
(4+5): An amount of 346 mg (3.05 mmol) cyclohexanone oxime
was dissolved in 0.49 mL of dichloromethane at room temperature
followed by dropwise addition of 1.306 g (4.59 mmol) of Ti-
(OiPr)4. The reaction mixture was stirred for 20 min. Colorless
crystals of 4+5 were obtained from the yellow solution after one
day beside crystals of 5. The crystals were washed with several por-
Figure 11. Numbering of the carbon atoms of cyclohexanone, cy-
clopentanone and acetoximate ligands.
1
FT-IR spectra were recorded on a Bruker Tensor 27 working in
ATR MicroFocusing MVP-QL with a ZnSe crystal or in dichloro-
methane solution, using OPUS version 4.0 software for analysis.
Reliable elemental analyses were not obtained due to the high
moisture sensitivity of the complexes.
tions of hexane at –20 °C and dried in vacuo. H NMR (CDCl3,
20 °C): δ = 4.45 (m, 1 H, CH2Me), 2.55 (m, 1 H, C2H), 2.32 (m, 1
H, C6H), 1.58 (s, 3 H, C3–5H), 1.17 (d, J = 6.2 Hz, 5 H, CH3), 1.03
(d, J = 6.1 Hz, 1 H, CH3) ppm. 13C{1H} NMR (CDCl3, 20 °C): δ
= 152.8 (C=N), 77.2 (CHMe2), 32.4 (C6), 28.6 (C2), 25.8/26.4
(C3–5), 25.7/26.9 (CH ) ppm. IR (CH Cl ): ν = 2971 (s), 2936 (s),
˜
3
2
2
Synthesis of [Ti(OiPr)2(ON=C5H8)2]2 (1): An amount of 389 mg
(4.93 mmol) cyclopentanone oxime was dissolved in 0.79 mL of
dichloromethane at room temperature followed by dropwise ad-
dition of 701 mg (2.47 mmol) of Ti(OiPr)4. The pale yellow reac-
tion mixture was stirred for 5 min. Colorless crystals were obtained
from the solution after two days which were washed with several
portions of pentane at –20 °C and dried in vacuo; yield 383 mg
(43%). 1H NMR (CDCl3, 20 °C): δ = 4.50 (q, J = 6.0 Hz, 1 H,
CHMe2), 2.52 (m, 2 H, C2H), 2.42 (m, 2 H, C5H), 1.76 (s, 4 H,
2863 (s), 1652 (w), 1449 (m), 1377 (m), 1363 (m), 1331 (m), 1162
(s), 1123 (vs), 1075 (w), 999 (s), 949 (m), 901 (w), 851 (sh), 619 (m),
535 (m) cm–1.
Synthesis of [Ti(OiPr)2(ON=C6H10)2]2 (5): An amount of 339 mg
(3.00 mmol) cyclohexanone oxime was dissolved in 0.50 mL of
dichloromethane at room temperature followed by dropwise ad-
dition of 423 mg (1.49 mmol) of Ti(OiPr)4. The reaction mixture
was stirred for 20 min. Colorless crystals were obtained from the
yellow solution after one day which were washed with several por-
tions of hexane at –20 °C and dried in vacuo; yield 452 mg (78%).
1H NMR ([D8]toluene, 20 °C): δ = 4.75 (q, J = 6.1 Hz, 3 H,
CHMe2), 4.41 (q, J = 6.1 Hz, 1 H, CHMe2), 2.76 (t, J = 6.7 Hz, 3
H, C2H), 2.60 (t, J = 7.2 Hz, 5 H, C2H), 2.50 (t, J = 6.3 Hz, 5 H,
C6H), 2.32 (t, J = 5.8 Hz, 3 H, C6H), 1.62 (s, 6 H, C3–5H), 1.49 (d,
J = 6.2 Hz, 16 H, CH3), 1.30 (s, 18 H, C3–5H), 1.11 (d, J = 6.0 Hz,
8 H, CH3) ppm. 13C{1H} NMR ([D8]toluene, 20 °C): δ = 146.2/
148.8 (C=N), 72.9/76.3 (CHMe2), 31.9 (C6), 28.1 (C2), 25.8/26.0
C
3,4H), 1.17 (d, J = 5.5 Hz, 4 H, CH3), 1.06 (d, J = 6.1 Hz, 2 H,
CH3) ppm. 13C{1H} NMR (CDCl3, 20 °C): δ = 158.3 (C=N), 76.2/
77.7 [CH(CH3)2], 30.1 (C5), 29.2 (C2), 24.9 (CH3), 24.6/24.8 (C3,4),
23.7 (CH ) ppm. IR (CH Cl ): ν = 2970 (s), 2874 (s), 1668 (m),
˜
3
2
2
1634 (w), 1453 (m), 1426 (m), 1376 (m), 1362 (m), 1330 (m), 1214
(w), 1162 (s), 1125 (vs), 1073 (w), 998 (vs), 947 (s), 851 (sh), 814
(w), 623 (s), 582 (s), 567 (s) cm–1.
Synthesis of [Ti(OiPr)2(ON=CMe2)2]2 (2): An amount of 156 mg
(2.13 mmol) acetoxime was dissolved in 0.30 mL of dichlorometh-
ane at room temperature followed by dropwise addition of 307 mg
(1.08 mmol) of Ti(OiPr)4. A white crystalline solid precipitated im-
mediately which was re-dissolved by addition of 0.40 mL of di-
chloromethane. Colorless crystals were obtained from the yellow
solution after one day which were washed with several portions of
hexane at –20 °C and dried in vacuo; yield 126 mg (30%). 1H NMR
(CDCl3, 20 °C): δ = 4.60 (q, J = 5.9 Hz, 1 H, CHMe2), 2.07 (s, 3
H, C2H), 2.04 (s, 3 H, C3H), 1.22 [d, J = 5.2 Hz, 3 H, CH(CH3)2],
1.09 [d, J = 5.8 Hz, 3 H, CH(CH3)2] ppm. 13C{1H} NMR (CDCl3,
20 °C): δ = 147.7 (C=N), 76.3 (CHMe2), 25.7/26.3 [CH(CH3)2],
(C3–5), 25.0/26.7 (CH ) ppm. IR (CH Cl ): ν = 2970 (s), 2940 (s),
˜
3
2
2
2861 (s), 1655 (w), 1449 (sh), 1377 (m), 1326 (w), 1129 (m), 1074
(w), 1002 (s), 948 (m), 902 (w), 847 (w), 589 (s), 537 (m) cm–1.
Synthesis of [Ti(OEt)2(ON=C6H10)2]2 (6): An amount of 511 mg
(4.51 mmol) cyclohexanone oxime was dissolved in 0.75 mL of
dichloromethane at room temperature followed by dropwise ad-
dition of 518 mg (2.27 mmol) of Ti(OEt)4 and stirring for 30 min.
A fawn solid precipitated upon evaporation of the solvent which
was re-dissolved in 0.25 mL of CH2Cl2 upon heating. Colorless
crystals were obtained from the yellow solution after 30 min which
were washed with several portions of hexane at –20 °C and dried
21.7 (C2H), 18.5 (C3H) ppm. IR (CH Cl ): ν = 2970 (s), 2874 (s),
˜
2
2
1667 (m), 1453 (m), 1426 (w), 1375 (m), 1362 (m), 1330 (w), 1214
(w), 1161 (s), 1125 (vs), 1073 (w), 998 (vs), 947 (m), 851 (sh), 814
(w), 623 (m), 582 (s), 567 (m) cm–1.
1
in vacuo; yield 541 mg (66%). H NMR (CDCl3, 20 °C): δ = 4.54
(q, J = 6.0 Hz, 1 H, CH2Me), 2.55 (m, 4 H, C2H), 2.32 (m, 4 H,
C6H), 1.58 (s, 12 H, C3–5H), 1.15 (d, J = 5.0 Hz, 3 H, CH3), 1.03
(d, J = 5.8 Hz, 3 H, CH3) ppm. 13C{1H} NMR (CDCl3, 20 °C): δ
= 151.0/152.8 (C=N), 76.1/77.2 (CH2CH3), 32.2/32.4 (C6), 28.6
Synthesis of [Ti(OiPr)2(ON=C(Me)Et)2]2 (3): An amount of
530 mg (6.08 mmol) ethyl methyl ketoxime was dissolved in
0.45 mL of dichloromethane at room temperature followed by
dropwise addition of 864 mg (3.04 mmol) of Ti(OiPr)4. A colorless
(C2), 25.8 (C3–5), 25.7/26.9 (CH ) ppm. IR (CH Cl ): ν = 2969 (s),
˜
3
2
2
2941 (s), 2860 (s), 1656 (m), 1449 (m), 1422 (m), 1376 (w), 1161
3338
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Eur. J. Inorg. Chem. 2009, 3333–3340