Bis(Cyclopentadienyl)Titanium Complexes
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starting material and any insoluble impurities. The filtrate was
concentrated under vacuum to ca. 3 cm3 and hexane (20 cm3) was
added to precipitate the product as a purple solid (0.154 g, 38%).
Microanalysis: Found (calcd for TiC28H32S2) C 70.21 (69.98), H
6.68 (6.71)%. 1H NMR (CDCl3) δ: 7.54-7.51 (d, 2H, aromatics),
7.41-7.38 (d, 2H, aromatics), 6.28, (s, 10H, cp groups), 1.50 (s,
18H, t-Bu groups). 13C NMR (CDCl3) δ: 139.6 (quaternary
aromatic), 139.1 (quaternary aromatic), 132.8 (quaternary aromatic),
125.8 (aromatic C-H), 121.9 (aromatic C-H), 120.2 (cp groups),
35.6 (quaternary t-Bu), 28.2 (Me groups). Selected IR data (KBr)
ν/cm-1: 1354 (m), 1242 (m), 1014 (s) and 819 (s). FAB+ MS: m/z
480 [M]+.
precipitate the product as a green solid. Yield 0.069 g (21%). H
NMR (CD2Cl2) δ: 7.71-7.68 (dd, 2H, aromatics), 7.38-7.31 (td,
2H, aromatics), 7.25-7.16 (td, 2H, aromatics), 7.02-6.98 (dd, 2H,
aromatics), 6.17 (s, 10H, cp groups). 13C NMR (CD2Cl2) δ: 151.8,
142.3 (both 2C, quaternary aromatics), 133.5, 129.8, (both 2C,
aromatic C-H), 128.8, 128.2 (both 2C, quaternary aromatics),
127.3, 125.9 (both 2C, aromatic C-H), 114.7 (10C, Cp groups).
FAB+ MS: m/z 394 [M]+.
Titanocene 1,1′-dithiolato[2,2′]binaphthalene (6). A mixture
of titanocene dicarbonyl (200 mg, 0.86 mmol) and 13,14-dithia-
picene (270 mg, 0.86 mmol) in toluene was stirred for 1 h. The
resulting green solution was filtered through a small Celite pad to
remove any unreacted starting material and any insoluble impurities.
The filtrate was removed under vacuum and the remaining solid
was purified by chromatography through silica, using dichlo-
romethane as an elutant. The green layer was collected, dried, and
recrystallized from toluene to give dark crystals. Yield 0.091 g
Titanocene 1,8-dithiolato-5,6-dihydroacenaphthalene (3). A
mixture of titanocene dicarbonyl (200 mg, 0.86 mmol) and 5,6-
dihydroacenaphtho[5,6-c,d]-1,2-dithiole (185 mg, 0.86 mmol) in
toluene was stirred for 1 h. The resulting red solution was filtered
through a small Celite pad to remove any unreacted starting material
and any insoluble impurities. The filtrate was concentrated under
vacuum to ca. 3 cm3 and the product started to precipitate as a red
solid (0.270 g, 80%). Microanalysis: Found (calcd for TiC22H18S2)
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(21.5%). H NMR (CD2Cl2) δ: 8.66 (d, 2H, aromatics), 7.92 (d,
2H, aromatics), 7.72 (d, 2H, aromatics), 7.68-7.58 (m, 4H,
aromatics), 7.14 (d, 2H, aromatics), 6.14 (s, 10H, cp groups). 13C
NMR (CD2Cl2) δ: 140.6, 134.3, 133.2 (all 1C, quaternary aromat-
ics), 128.6, 128.0, 127.3, 125.9, 125.8, 125.7 (all 1C, aromatic
C-H), 114.4 (10C, cp groups).
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C 68.34 (67.0), H 5.19 (4.6)%. H NMR (CD2Cl2) δ: 7.20 (m,
4H, aromatics), 6.8-6.0 (broad d, 10H, cp groups), 3.31 (s, 4H,
CH2 × 2). 13C NMR (CD2Cl2) δ: 144.0 (quaternary aromatic),
143.4 (quaternary aromatic), 140.8 (quaternary aromatic), 132.7 (cp
groups), 118.8 (aromatic C-H), 114.7 (aromatic C-H), 30.0 (CH2).
Selected IR data (KBr) ν/cm-1: 1398 (m), 1231 (m), 1016 (s) and
825 (s). EI+ MS: m/z 394 [M]+.
Titanocene 1-sulfinato-8-thiolato-naphthalene (7). A mixture
of titanocene dicarbonyl (211 mg, 0.90 mmol) and naphtho-[1,8-
cd]-1,2-dithiole-1,1-dioxide (200 mg, 0.90 mmol) in toluene was
stirred for 1 h. The resulting dark red solution was filtered through
a small Celite pad to remove any unreacted starting material and
any insoluble impurities. The filtrate was concentrated under
vacuum to ca. 3 cm3 and hexane (30 cm3) was added to precipitate
the product as a dark red-purple solid (0.161 g, 45%). Found (calcd
Titanocene 1,8-dithiolato-acephenanthrylene (4). A mixture
of titanocene dicarbonyl (200 mg, 0.86 mmol) and 4,5-dithioa-
cephenanthrylene (205 mg, 0.86 mmol) in toluene was allowed to
stir for 1 h. The resulting dark solution was filtered through a small
Celite pad to remove any unreacted starting material and any
insoluble impurities. The filtrate was dried under vacuum, dissolved
in a minimum volume of dichloromethane, and hexane (20 cm3)
was added to precipitate the product as a brown solid (0.066 g,
19%). Microanalysis: Found (calcd for TiC24H18S2) C 69.14 (68.9),
H 4.09 (4.3)%.1H NMR (CD2Cl2) δ: 8.48 (m, 2H, aromatics),
7.71-7.35 (m, 6H, aromatics), 6.31 (s, 10H, cp groups). 13C NMR
(CD2Cl2) δ: 114.9 (cp groups), 133.4, 131.3, 127.2, 127.1, 126.0,
124.8, 123.1, 120.8 (all aromatic C-H), 128.5, 125.5, 122.9, 118.5,
118.2, 112.6 (all quaternary aromatics). Selected IR data (KBr)
ν/cm-1: 1437 (m), 1201 (m), 1016 (s) and 819 (s). FAB+ MS: m/z
418 [M]+.
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for (TiC20H16S2O2)2‚C7H8) C 62.92 (63.22), H 4.51 (4.52)%. H
NMR (CD2Cl2) δ: 8.42 (dd, 1H, aromatic), 8.01 (dd, 1H, aromatic),
7.87 (dd, 1H, aromatic), 7.74 (dd, 1H, aromatic), 7.57 (dt, 2H,
aromatics), 6.52 (s, 5H, cp group) and 5.75 (s, 5H, cp group). 13
C
NMR (CD2Cl2) δ: 148.1, 143.0, 135.5, 133.4, 133.0, 131.7, 129.2,
125.7, 125.6, 123.4 (all aromatics) and 117.0 (cp groups). Selected
IR data (KBr) ν/cm-1: 3057 (m), 1445 (m), 1334 (m), 1092 (s),
1072 (s), 1054 (s) and 761 (s). Mass Spec (FAB): (M + H)+ 401.
Method B. A mixture of titanocene dicarbonyl (284 mg, 1.21
mmol) and naphtho-[1,8-cd]-1,2-dithiole-1,1,2-trioxide (290 mg,
1.21 mmol) in toluene was stirred for 1 h. The resulting dark red
solution was filtered through a small Celite pad to remove any
unreacted starting material and any insoluble impurities. The filtrate
was concentrated under vacuum to ca. 3 cm3 and hexane (20 cm3)
was added to precipitate the product as a dark red-purple solid
(0.197 g, 40%). Selected IR data (KBr) ν/cm-1: 3065 (m), 1445
(m), 1330 (m), 1092 (s) and 759 (s). Mass Spec (FAB): (M +
H)+ 401.
Titanocene 2-sulfinato 2′-thiolato biphenyl (8). A mixture of
titanocene dicarbonyl (189 mg, 0.81 mmol) and dibenzo[ce]-1,2-
dithiine-5,5-dioxide (200 mg, 0.81 mmol) in toluene was stirred
for 1 h. The resulting brown solution was filtered through a small
Celite pad to remove any unreacted starting material and any
insoluble impurities. The solvent was removed under reduced
pressure and the brown solid was purified by chromatography
through silica. Dichloromethane was used to elute a green layer
which was characterized as complex 1 and then acetone was used
to elute an orange layer. The orange layer was recrystallized from
toluene. Yield 0.068 g (20%). Microanalysis: Found (calcd for
(TiC22H18S2O2)3C7H8) C 63.33 (63.93), H 4.68 (4.56)%. 1H NMR
(CD2Cl2) δ: 7.83-7.16 (m, 8H, aromatics), 6.25 (s, 5H, cp group),
6.08 (s, 5H, cp group). 13C NMR δ: 133.4, 130.7, 130.2, 129.1,
Titanocene 2,2′-dithiolato biphenyl (5). A mixture of titanocene
dicarbonyl (216 mg, 0.93 mmol) and dibenzo[ce]-1,2-dithiine (200
mg, 0.93 mmol) in toluene was stirred for 1 h. The resulting green
solution was filtered through a small Celite pad to remove any
unreacted starting material and any insoluble impurities. The filtrate
was concentrated under vacuum to ca. 3 cm3 and hexane (20 cm3)
was added to precipitate the product as a green solid. Yield 0.302
g (83%). Microanalysis: Found (calcd for TiC22H18S2) C 66.70
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(67.0), H 4.80 (4.6)%. H NMR (CDCl3) δ: 7.74-7.71 (dd, 2H,
aromatics), 7.39-7.32 (td, 2H, aromatics), 7.25-7.17 (td, 2H,
aromatics), 7.09-7.06 (dd, 2H, aromatics), 6.17 (s, 10H, cp groups).
13C NMR (CDCl3) δ: 151.1, 142.0 (both 2C, quaternary aromatics),
133.4, 130.0, 127.5, 126.3 (all 2C, aromatic C-H), 114.8 (10C,
Cp groups). FAB+ MS: m/z 394 [M]+.
Method B. A mixture of titanocene dicarbonyl (200 mg, 0.86
mmol) and dibenzo[ce]-1,2-dithiine-5-oxide (198 mg, 0.86 mmol)
in toluene was stirred overnight. The resulting green solution was
filtered through a small Celite pad to remove any unreacted starting
material and any insoluble impurities. The filtrate was concentrated
under vacuum to ca. 3 cm3 and hexane (20 cm3) was added to
Inorganic Chemistry, Vol. 44, No. 8, 2005 2717