ꢀ
M.C. Mancilla-Gonzalez et al. / Journal of Organometallic Chemistry 770 (2014) 35e41
40
Table 6
Ar), 133.4 (Cipso), 133.9 (p-Ar), 177.3 (CeO), 202.9 ppm (C]S). MS-
EI (70 eV) m/z: 258(20) [C10H9OS2Ti]þ. Anal. Calcd. for
Selected bond length (Å) and angles (ꢁ) for complexes 6e10.
C15H14Cl2OS2Ti: C, 45.80; H, 3.56; S, 16.28. Found: C, 46.29; H, 3.95;
6
7
8
9
10
S, 15.83.
Ti(1)eCpcentroid
Ti(1)eO(1)
Ti(1)eS(1)
Ti(1)eCl(1)
Ti(1)eCl(2)
C(1)eC(2)
C(2)eC(3)
S(1)eC(1)
O(1)eC(3)
2.033
2.041
2.049
2.041
2.048
1.918(1)
2.509(1)
2.335(1)
2.358(1)
1.407(3)
1.384(3)
1.692(2)
1.300(2)
1.740(2)
1.799(2)
80.1(1)
1.909(1)
2.514(1)
2.366(1)
2.355(1)
1.401(2)
1.376(2)
1.686(2)
1.299(2)
1.745(2)
1.794(2)
81.1(1)
1.904(1)
2.503(1)
2.353(1)
2.358(1)
1.409(2)
1.383(2)
1.697(2)
1.305(2)
1.738(2)
1.797(2)
80.0(1)
1.911(1)
2.517(1)
2.351(1)
2.359(1)
1.406(2)
1.372(2)
1.683(2)
1.300(2)
1.741(2)
1.796(2)
80.9(1)
1.908(2)
2.525(1)
2.346(1)
2.340(1)
1.408(4)
1.381(3)
1.693(3)
1.300(3)
1.738(2)
1.789(2)
79.0(1)
Compound 7. Dark yellow solid. Yield 79% (0.51 g, 1.25 mmol). Mp:
ꢀ1
164 ꢁC (dec). IR (ATR, cm ): v 3105 w, 1520 m, 1482 s, 1263 s (C]S),
~
1016 m, 823 s (CeS), 725 m. 1H NMR (300 MHz, CDCl3, 25 ꢁC):
d
2.45
(s, 3H, p-CH3), 2.73 (s, 3H, SCH3), 6.68 (s, 5H, C5H5), 7.33 (s, 1H, C]
CH), 7.35 (d, 2H, J ¼ 8.2 Hz, m-Ar), 7.93 ppm (d, 2H, J ¼ 8.2 Hz, o-Ar).
13C NMR (75 MHz, CDCl3, 25 ꢁC):
d 17.4 (SCH3), 55.6 (p-CH3), 109.6
S(2)eC(1)
S(2)eC(10)
(C]CH), 122.1 (C5H5), 128.5 (m-Ar), 130.1 (o-Ar), 131.1 (Cipso), 144.8
(p-Ar), 177.6 (CeO), 201.9 (C]S) ppm. MS-EI (70 eV) m/z: 272(9)
[C11H11OS2Ti]þ. Anal. Calcd. for C16H16Cl2OS2Ti: C, 47.29; H, 3.69; S,
15.76. Found: C, 47.29; H, 4.13; S, 14.86.
O(1)eTi(1)eS(1)
Cl(1)eTi(1)eCl(2)
O(1)eTi(1)eCl(1)
S(1)eTi(1)eCl(1)
O(1)eTi(1)eCl(2)
S(1)eTi(1)eCl(2)
S(1)eC(1)eC(2)
Ti(1)eO(1)eC(3)
Ti(1)eS(1)eC(1)
C(1)eC(2)eC(3)
C(2)eC(3)eO(1)
S(1)eC(1)eS(2)
88.1(1)
86.4(1)
88.7(1)
85.2(1)
89.4(1)
85.4(1)
89.2(1)
85.3(1)
90.0(1)
84.7(1)
136.9(1)
138.4(1)
76.1(1)
127.4(1)
141.0(1)
109.5(1)
124.6(2)
121.9(2)
120.1(1)
141.1(1)
138.1(1)
78.1(1)
128.1(1)
150.1(1)
111.7(1)
125.0(1)
122.4(1)
119.3(1)
141.2(1)
136.2(1)
77.4(1)
127.8(1)
144.8(1)
109.7(1)
124.1(2)
121.2(2)
119.6(1)
141.2(1)
138.4(1)
78.0(1)
128.0(1)
149.5(1)
111.9(1)
125.0(1)
122.6(1)
119.6(1)
143.7(1)
133.9(1)
78.9(3)
127.3(2)
142.9(1)
108.5(1)
123.9(2)
121.8(2)
120.6(2)
Compound 8. Dark yellow-orange solid.ꢀ1Yield 66% (0.35
g
0.83 mmol). Mp: 167 ꢁC (dec). IR (ATR, cm ): v 3008 w, 1481 m,
1440 m, 1246 s (C]S), 1021 m, 823 s (CeS), 730 w. 1H NMR
~
(300 MHz, CDCl3, 25 ꢁC):
d 2.73 (s, 3H, OCH3), 3.92 (s, 3H, SCH3),
6.68 (s, 5H, C5H5), 7.04 (d, 2H, J ¼ 8.7 Hz, m-Ar), 7.30 (s, 1H, C]CH),
8.03 ppm (d, 2H, J ¼ 9 Hz, o-Ar). 13C NMR (75 MHz, CDCl3, 25 ꢁC):
d
17.3 (SCH3), 55.6 (OCH3), 109.3 (C]CH), 114.8 (o-Ar), 119.5 (Cipso),
121.6 (C5H5), 122.1 (m-Ar), 164.2 (p-Ar), 177.4 (CeO), 200.5 ppm
(C]S). MS-EI (70 eV) m/z: 288(17) [C11H11O2S2Ti]þ. Anal. Calcd. for
(p-Ar), 169.6 (CeO), 215.7 (C]S). Anal. Calcd for C11H12O2S2: C,
54.97; H, 5.03; S, 26.68. Found: C, 54.81; H, 5.03; S, 26.44.
C16H16Cl2O2S2Ti: C, 45.39; H, 3.78; S, 15.13. Found: C, 44.98, H, 3.83,
S, 14.38.
Compound 4. Crystalline yellow solid. ꢀY1 ield 62% (3.12 g,
12.76 mmol). Mp: 75e76 ꢁC. IR (ATR, cm ): v 1582 s, 1551 m,
Compound 9. Dark yellow solid. Yield 53% (0.31 g, 0.72 mmol). Mp:
~
ꢀ1
168 ꢁC (dec). IR (ATR, cm ):v 3105 w, 1514 s, 1471 s, 1251 s (C]S),
1252 m (C]S), 1051 m (CeO), 775 s (CeS). 1H NMR (300 MHz,
~
1024 w, 833 s (CeS), 723 m. 1H NMR (300 MHz, CDCl3, 25 ꢁC):
d
2.75
CDCl3, 25 ꢁC):
d
2.67 (s, 3H, SCH3), 6.91 (s, 1H, C]CH), 7.44 (d, 2H,
J ¼ 8.7 Hz, m-Ar), 7.81 (d, 2H, J ¼ 8.7 Hz, o-Ar), 15.06 ppm (s, 1H,
OH). 13C RMN (75 MHz, CDCl3, 25 ꢁC):
17.2 (SCH3), 107.7 (C]CH),
(s, 3H, SCH3), 6.69 (s, 5H, C5H5), 7.29 (s, 1H, C]CH), 7.52 (d, 2H,
J ¼ 8.5 Hz, m-Ar), 7.97 ppm (d, 2H, J ¼ 8.5 Hz, o-Ar). 13C NMR
d
(75 MHz, CDCl3, 25 ꢁC):
d 17.6 (SCH3), 109.5 (C]CH), 122.3 (C5H5),
127.9 (m-Ar), 129.1 (o-Ar), 132.7 (Cipso), 138 (p-Ar), 167.8 (CeO)
217.6 ppm (C]S). Anal. Calcd. for C10H9ClOS2: C, 49.08; H, 3.68; S,
26.18. Found: C, 48.92; H, 3.75; S, 26.14.
128.5 (Cipso), 129.6 (o-Ar), 132.6 (m-Ar), 133.0 (p-Ar), 175.9 (CeO)
203.6 ppm (C]S). MS-EI (70 eV) m/z: 292(14) [C10H8ClOS2Ti]þ.
Anal. Calcd. for C15H13Cl3OS2Ti: C, 42.10; H, 3.04; S, 14.97. Found: C,
41.96; H, 3.21; S, 14.46.
Compound 5. Crystalline yellow soꢀli1d. Yield 60% (2.22 g,
7.68 mmol). Mp: 88e90 ꢁC. IR (ATR, cm ): v 1579 s, 1552 m, 1229 s
~
(C]S), 1048 m (CeO), 752 s (CeS). 1H NMR (300 MHz, CDCl3,
Compound 10. Dark yellow solid. Yield 78% (0.40 g, 0.84 mmol).
ꢀ1
Mp: 161 ꢁC (dec). IR (ATR, cm ): v 3102 w,1512 s,1471 s,1251 s (C]
25 ꢁC):
d
2.66 (s, 3H, SCH3), 6.91 (s, 1H, C]CH), 7.59 (d, 2H,
J ¼ 8.5 Hz, m-Ar), 7.73 (d, 2H, J ¼ 8.5 Hz, o-Ar),15.05 ppm (s,1H, OH).
13C RMN (75 MHz, CDCl3, 25 ꢁC):
17.2 (SCH3), 107.6 (C]CH), 126.5
~
S), 1021 w, 831 s (CeS), 730 m. 1H NMR (300 MHz, CDCl3, 25 ꢁC):
d
2.75 (s, 3H, SCH3) 6.69 (s, 5H, C5H5), 7.29 (s, 1H, C]CH), 7.68 (d,
d
2H, J ¼ 8.7 Hz, m-Ar), 7.89 ppm (d, 2H, J ¼ 8.7 Hz, o-Ar). 13C NMR
(m-Ar), 128.1 (o-Ar), 132.1 (Cipso), 133.2 (p-Ar), 167.8 (CeO)
217.6 ppm (C]S). Anal. Calcd. for C10H9BrOS2: C, 41.52; H, 3.11; S,
22.14. Found: C, 41.54; H, 3.20; S, 22.35.
(75 MHz, CDCl3, 25 ꢁC):
d 17.6 (SCH3), 109.5 (C]CH), 122.3 (C5H5),
128.5 (o-Ar), 129.6 (m-Ar), 132.7 (Cipso), 133.0 (p-Ar), 175.9 (CeO),
203.6 ppm (C]S). MS-EI (70 eV) m/z: 336(7) [C10H8BrOS2Ti]þ. Anal.
Calcd. for C15H13BrCl2OS2Ti: C, 38.13; H, 2.75; S, 13.56. Found, C,
37.47; H, 2.90; S, 12.68.
General procedure for the preparation of 6e10
Triethylamine (0.21 mL, 1.50 mmol) was added to a solution of
the ligand (1.00 mmol) in THF (15 mL) at ambient temperature and
stirred for 1 h. A solution of CpTiCl3 (0.22 g, 1.00 mmol) in THF
(5 mL) was then added and the solution was allowed to stir for 2 h.
The reaction mixture was filtered and the volume of the solution
was reduced to 5 mL, after which hexane (10 mL) was added to
obtain a precipitate. The solid was filtered and washed with hexane
(3 ꢂ 5 mL).
Acknowledgments
M.M.-C. is grateful to the DGAPA-UNAM (PAPIIT Grant IN210313)
for financial support. M.C.M.-G. thanks the CONACyT for the MSc
fellowship (273697). The authors acknowledge N. Zavala-Segovia,
~
A. Núnez-Pineda and L. Triana-Cruz for their technical assistance.
Compound 6. Dark yellow solid. Yield 66% (0.35 g, 0.89 mmol).
Appendix A. Supplementary data
ꢀ1
Mp: 118 ꢁC (dec). IR (ATR, cm ): v 3100 w, 1590 w, 1557 w, 1261 s
~
(C]S), 1020 w, 818 s (CeS), 728 m (CeH). 1H NMR (300 MHz,
The following is the supplementary data related to this article:
CCDC 1011077e1011085 (for 1, 3e10) contain the supplemen-
tary crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
CDCl3, 25 ꢁC):
d 2.74 (s, 3H, SCH3), 6.69 (s, 5H, C5H5), 7.35 (s, 1H,
C]CH), 7.53 (t, 2H, J ¼ 7.2 Hz, m-Ar), 7.59 (t, 1H, J ¼ 7.8 Hz, p-Ar),
8.05 ppm (d, 2H, J ¼ 7.2 Hz, o-Ar). 13C NMR (75 MHz, CDCl3, 25 ꢁC):
d
17.5 (SCH3), 109.8 (C]CH), 122.2 (C5H5), 128.3 (m-Ar), 129.3 (o-