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J.-L. Li et al. / Inorganica Chimica Acta 368 (2011) 231–236
Scheme 1. The preparation process of complexes 1–5.
cylic acid [32] was synthesized according to the literature. Ben-
zene, dichloromethane and hexane were dried before use.
IR spectra were recorded on an FT-IR450 spectrometer in the
spectral range 4000–400 cmꢀ1 with the samples in the form of
KBr pellets. The 1H NMR spectra were recorded on AVANCE
300 MHz with TMS as internal standard. Elemental analyses were
performed on a Varian EL III elemental analyzer. UV–Vis spectra
were recorded on a TU-1901 spectrometer.
C
17H14O2STi: C, 61.83; H, 4.27. Found: C, 61.80; H, 4.22%. 1H
NMR (300 MHz, SO(CD3)2) d values (ppm): 6.48 (s, 10H, 2ꢁ
C5H5); 7.22–8.42 (m, 4H, 4ꢁ ArH). IR (KBr) : 3105, 1614, 1429,
1290, 1017, 823 cmꢀ1
m
.
2.2.4. (g5-C5H5)2Ti(O,O0)(OCC6H4) (3)
Complex 3 was prepared in the same way as 1. The dark brown
solid was recrystallized from a mixture of dichloromethane–hex-
ane to give dark brown crystals (92.1% yield); mp 186–187 °C. Anal.
Calc. for C17H14O3Ti: C, 64.99; H, 4.49. Found: C, 64.10; H, 4.46%. 1H
NMR (300 MHz, CDCl3) d values (ppm): 6.54 (s, 10H, 2ꢁ C5H5);
2.2. Syntheses
2.2.1. 5,50-Dithiodisalicylic acid (5,50-DTDS)
6.61–8.10 (m, 4H, 4ꢁ ArH). IR (KBr)
m: 3106, 1621, 1450, 1325,
1014, 818 cmꢀ1
.
Concentrated hydrochloric acid (30 mL) was added to a solid
mixture of 5-chlorosulfonyl-salicylic acid (4.5 g) and tin particles
(14 g) in an ice bath. After stirring for 12 h, the reaction system
was heated to boil until there was no precipitate present, then
cooled again with ice-bath and filtered. The resulting solid was dis-
solved by ethyl ether, the insoluble precipitate was filtered off, and
the filtrate was dried and recrystallized from Et2O–H2O to give
5,50-DTDS (93.25%, yield) as yellow solid; mp 224–226 °C. Anal.
Calc. for C14H10O6S2: C, 49.70; H, 2.98. Found: C, 48.08; H, 2.75%.
1H NMR (300 MHz, CD3COCD3) d values (ppm): 7.02 (d, 1H); 7.76
2.2.5. (g5-C5H5)2Ti(O,O0)(5-Cl-OCC6H4) (4)
Complex 4 was prepared in the same way as 1. The brown solid
was recrystallized from a mixture of dichloromethane–hexane to
give brown crystals (91.1% yield); mp 214–216 °C. Anal. Calc. for
C
17H13ClO3Ti: C, 58.57; H, 3.76. Found: C, 58.45; H, 3.71%. 1H
NMR (300 MHz, CDCl3) d values (ppm): 6.57 (s, 10H, 2ꢁ C5H5);
6.64–8.10 (m, 3H, ArH). IR (KBr) : 3096, 1618, 1403, 1306, 1017,
820 cmꢀ1
m
.
(d, 1H); 8.02 (s, 1H). IR (KBr) m: 3064–2602, 1668, 1599, 1572,
1473, 1445, 1320, 1290, 1207, 1146, 1077, 881 cmꢀ1
.
2.2.6. (g5-C5H5)2Ti(O,O0)(5-Br-OCC6H4) (5)
Complex 5 was prepared in the same way as 1. The brown solid
was recrystallized from a mixture of dichloromethane–hexane to
give brown crystals (84.9% yield); mp 208–210 °C. Anal. Calc. for
2.2.2. Cp2Ti(2-OH-5-S-O2CC6H3)2 (1)
NaOH (0.10 g, 2.5 mmol) and ethanol (2 mL) were added to the
mixture of Cp2TiCl2 (0.248 g, 1.0 mmol) and 5,50-DTDS (0.384 g,
1.0 mmol), which were dissolved in CHCl3 (40 mL)/Et2O (10 mL),
previously. After stirring for 30 min at room temperature, the reac-
tion solution was dried with anhydrous MgSO4 and filtered. The fil-
trate was concentrated in vacuo to give an orange solid. The
complex was purified by recrystallinization from dichlorometh-
ane–hexane yielded orange crystalline solid (77.7% yield); mp
240–242 °C (dec.). Anal. Calc. for C24H18O6S2Ti: C, 56.04; H, 3.53.
Found: C, 55.73; H, 3.52%. 1H NMR (300 MHz, CDCl3) d values
(ppm): 6.69 (s, 10H, 2ꢁ C5H5); 6.94 (d, 2H, ArH); 7.56 (d, 2H,
C
17H13BrO3Ti: C, 51.94; H, 3.33. Found: C, 51.83; H, 3.29%. 1H
NMR (300 MHz, CDCl3) d values (ppm): 6.57 (s, 10H, 2ꢁ C5H5);
6.68–8.13 (m, 3H, ArH). IR (KBr) : 3096, 1619, 1403, 1302, 1017,
820 cmꢀ1
m
.
2.3. X-ray crystal structure determination of 1
X-ray-quality crystals of Cp2Ti(2-OH-5-S-O2CC6H3)2 were ob-
tained directly from the preparations described above, and the
complex was stick-like crystals and remarkably stable when ex-
posed to air. The stick-like crystal complex was placed into a glass
capillary and sealed off. The X-ray data were collected at 273(2) K
on a Bruker Smart II 1000CCD diffractometer with graphite-mono-
ArH); 8.40 (s, 2H, ArH); 11.93 (s, 2H, OH). IR (KBr) m: 3425, 3109,
1629, 1563, 1467, 1386, 1330, 1287, 1240, 1215, 1107, 1072,
1018, 824, 717, 591, 548, 464, 416 cmꢀ1
.
chromated Mo K
a
radiation (k = 0.71073Å) using
x
ꢀ 2h scan tech-
2.2.3. (g5-C5H5)2Ti(S,O0)(OCC6H4) (2)
Complex 2 was prepared in the same way as 1. The deep green
solid was recrystallized from a mixture of benzene–hexane to give
deep green crystals (93.1% yield); mp 167–169 °C. Anal. Calc. for
nique. The structures were solved by direct method and refined on
F2 by full matrix least-squares with the Bruker’s SHELXL-97 [33] pro-
gram. All non-hydrogen atoms were refined anisotropically. All
hydrogen atoms were treated using a riding mode. The crystals