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1
57%. H-NMR (CDCl3): l 2.61 (s, 6H, CH3S), 6.61,
6.66 (s, s, 2H, 2H, H4 of pyrazole or CH2), 7.31, 7.75
(m, m, 6H, 4H, C6H5). IR (cm−1): wCO 2011.7 (s),
1908.6 (s), 1837.3 (s), 1821.2 (s); wpyrazole ring 1526.2 (m).
Anal. Calc. for C25H20N4O4S2W: C, 43.67; H, 2.91; N,
8.15. Found: C, 43.48; H, 3.19; N, 8.12%.
(s); wpyrazole ring 1576.0 (w). Anal. Calc. for
C27H24MoN4O6S2: C, 49.09; H, 3.64; N, 8.48. Found:
C, 48.79; H, 3.75; N, 8.39%.
2.5.3. Preparation of (3-methylthio-5-p-methoxy-
phenylpyrazol-1-yl-3%-p-methoxyphenyl-5%-methylthio-
pyrzol-1-yl)methane tetracarbonyltungsten (12) and
bis(3-methylthio-5-p-methoxyphenylpyrazol-1-yl)-
methane tetracarbonyltungsten (13)
2.5. Reaction of the mixture of 2–4 with M(CO)6
(M=Cr, Mo or W)
These compounds were obtained by the reaction of
the mixture of 2–4 with W(CO)6 as described above for
the reaction of 1 with Cr(CO)6, which were isolated by
column chromatography on silica using ether–hexane
(V:V=2:1) as eluent. Data for 12: 1H-NMR (CDCl3): l
2.27, 2.48 (s, s, 3H, 3H, CH3S), 3.85, 3.90 (s, s, 3H, 3H,
CH3O), 6.20, 6.29 (s, s, 1H, 1H, H4 of pyrazole), 6.20,
6.50 (d, d, 2H, CH2), 7.03–7.23, 7.35–7.49 (m, m, 4H,
4H, C6H4). IR (cm−1): wCO 2000.0 (m), 1876.1 (s),
1854.2 (s), 1832.1 (s); wpyrazole ring=1574.4 (w). Anal.
Calc. for C27H24N4O6S2W: C, 43.32; H, 3.21; N, 7.49.
Found: C, 43.01; H, 3.28; N, 7.78%. Data for 13:
1H-NMR (CDCl3): l 2.51 (s, 6H, CH3S), 3.63 (s, 6H,
CH3O), 6.17 (s, 2H, H4 of pyrazole), 6.32 (m, 2H,
CH2), 6.77, 6.96 (d, d, 4H, 4H, C6H4). IR (cm−1): wCO
2005.6 (m), 1889.4 (s), 1856.4 (s), 1825.6 (s); wpyrazole ring
1577.2 (w). Anal. Calc. for C27H24N4O6S2W: C, 43.32;
H, 3.21; N, 7.49. Found: C, 43.57; H, 3.51; N, 7.87%.
2.5.1. Preparation of (3-methylthio-5-p-methoxyphenyl-
pyrazol-1-yl-3%-p-methoxy phenyl-5%-methylthiopyrazol-
1-yl)methane tetracarbonylchromium (8) and
bis(3-methylthio-5-p-methoxyphenylpyrazol-1-yl)-
methane tetracarbonylchromium (9)
Compounds 8 and 9 were obtained by the reaction of
the mixture of 2–4 with Cr(CO)6 as described above for
the reaction of 1 with Cr(CO)6, which were isolated by
column chromatography on silica using ether–hexane
1
(V:V=2:1) as eluent. Data for 8: H-NMR (CDCl3): l
2.55, 2.59 (s, s, 3H, 3H, CH3S), 3.80, 3.85 (s, s, 3H, 3H,
CH3O), 6.28 (s, 2H, H4 of pyrazole), 6.57 (s, br, 2H,
CH2), 6.89–7.03, 7.65–7.56 (m, m, 4H, 4H, C6H4). IR
(cm−1): wCO 2004.6 (m), 1877.8 (vs, br) and 1839.3 (s);
wpyrazole ring 1576.1 (w). Anal. Calc. for C27H24CrN4O6S2:
C, 52.60; H, 3.90; N, 9.09. Found: C, 52.43; H, 3.59; N,
1
9.06%. Data for 9: H-NMR (CDCl3): l 2.50 (s, 6H,
CH3S), 3.80 (s, 6H, CH3O), 6.14 (m, 4H, H4 of pyrazole
and CH2), 6.74, 6.92 (m, m, 4H, 4H, C6H4). IR (cm−1):
wCO 2004.7 (m), 1878.2 (vs, br), 1839.2 (s); wpyrazole ring
1576.3 (w). Anal. Calc. for C27H24CrN4O6S2: C, 52.60;
H, 3.90; N, 9.09. Found: C, 52.54; H, 3.89; N, 9.36%.
The product of the reaction of 4 with Cr(CO)6 could
not be obtained.
2.6. Reaction of ligand 5 with M(CO)6 (M=Cr, Mo
or W)
2.6.1. Preparation of bis(3-methylthio-5-tert-
butylpyrazol-1-yl)methane tetracarbonylchromium (14)
This compound was obtained by the reaction of 5
with Cr(CO)6 as described above for the reaction of 1
with Cr(CO)6, which was isolated by column chro-
matography on silica using CH2Cl2–hexane (V:V=1:1)
2.5.2. Preparation of (3-methylthio-5-p-methoxyphenyl-
pyrazol-1-yl-3%-p-methoxy phenyl-5%-methylthiopyrazol-
1-yl)methanetetracarbonylmolybdenum (10) and
bis(3-methylthio-5-p-methoxyphenylpyrazol-1-yl)-
methanetetracarbonylmolybdenum (11)
1
as eluent. H-NMR (CDCl3): l 1.48 (s, 18H, C(CH3)3),
2.56 (s, 6H, CH3S), 6.09 (s, 2H, H4 of pyrazole), 6.40 (s,
br, 2H, CH2). IR (cm−1): wCO 2069.3 (m), 1988.1 (s),
1942.8 (vs, br); wpyrazole ring 1520.5 (s). Anal. Calc. for
C21H28CrN4O4S2: C, 48.84; H, 5.43; N, 10.85. Found:
C, 48.65; H, 5.58; N, 10.56%.
These compounds were obtained by the reaction of
the mixture of 2–4 with Mo(CO)6 as described above
for the reaction of 1 with Cr(CO)6, which were isolated
by column chromatography on silica using CH3CO2Et–
ether–hexane (V:V:V=1:1:3) as eluent. Data for 10:
1H-NMR (CDCl3): l 2.50, 2.51 (s, s, 3H, 3H, CH3S),
3.85, 3.87 (s, s, 3H, 3H, CH3O), 6.21, 6.29 (s, s, 1H, 1H,
H4 of pyrazole), 6.61 (s, br, 2H, CH2), 6.99–7.10,
7.28–7.50 (m, m, 4H, 4H, C6H4). IR (cm−1): wCO
2012.1 (m), 1883.4 (s), 1864.1 (s), 1836.4 (s); wpyrazole ring
1577.1 (w). Anal. Calc. for C27H24MoN4O6S2: C, 49.09;
H, 3.64; N, 8.48. Found: C, 48.94; H, 3.93; N, 8.46%.
2.6.2. Preparation of bis(3-methylthio-5-tert-butyl-
pyrazol-1-yl)methane tetracarbonylmolybdenum (15)
This compound was obtained by the similar method
as described above for 14 using Mo(CO)6 instead of
1
Cr(CO)6. H-NMR (CDCl3): l 1.47 (s, 18H, C(CH3)3),
2.46 (s, 6H, CH3S), 6.02 (s, 2H, H4 of pyrazole), 6.54 (s,
2H, CH2). IR (cm−1): wCO 2005.3 (m), 1879.2 (sh),
1863.7 (s), 1825.2 (s); wpyrazole ring 1511.2 (m). Anal. Calc.
for C21H28MoN4O4S2: C, 45.00; H, 5.00; N, 10.00.
Found: C, 44.64; H, 5.27; N, 9.78%.
1
Data for 11: H-NMR (CDCl3): l 2.48 (s, 6H, CH3S),
3.81 (s, 6H, CH3O), 6.13 (s, 2H, H4 of pyrazole), 6.28
(dd, 2H, CH2), 6.74, 6.93 (d, d, 4H, 4H, C6H4). IR
(cm−1): wCO 2012.3 (m), 1889.1 (s), 1870.3 (s), 1843.8