Organotitanoxane Halides
Inorganic Chemistry, Vol. 37, No. 20, 1998 5123
four-membered-ring Ti(µ-F)(µ-Cl)Sn intermediate, and organo-
titanoxane fluorides can be converted to the corresponding
chlorides and even further to the oxygen-free organotitanium
chlorides by using an excess of Me3SiCl. Due to the electron
deficiency of alkylaluminum compounds, they exhibit electro-
philic reactions with organotitanoxane fluorides, giving the
corresponding alkylaluminum adducts with different stoichio-
metric ratios. The adducts react further to yield novel alkylated
compounds.
decomposes slowly at -10 °C to give orange crystals, which were
characterized as [C
troscopy.
5
Me
5
Ti(µ-O)]
4
3 3
F[(µ-F)AlMe ] (2b) by NMR spec-
[
C
5
Me
5
Ti(µ-O)]
Me
4
F[(µ-F)AlMe
3
]
3
(2b). Compound 2b was prepared
by treating [C
5
5
Ti(µ-O)F]
4
(0.872 g, 1 mmol) with AlMe (1.5 mL,
3
3
mmol) in toluene (15 mL) at -10 °C for 10 min. The color changed
from yellow to orange during the addition. Orange crystals were
isolated in 60% (0.65 g) yield by cooling the solution (-10 °C). The
crystals decompose within 10 min at room temperature even under a
nitrogen atmosphere to afford an orange yellow solid which was
Finally, from our experience in this field, it is reasonable to
expect that an organotitanoxane-AlR3 compound may have
action and utility similar to those of the metallocene-methyl-
aluminoxane system. This investigation is in progress.
identified as [C
copy.
5
Me
5
Ti(µ-O)]
4
F
2
3 2
[(µ-F)AlMe ] (2c) by NMR spectros-
[
C
5
Me
by reacting [C
mmol) in toluene (15 mL) at 0 °C. The reaction mixture was stirred
5
Ti(µ-O)]
4
2
F [(µ-F)AlMe
]
3 2
(2c). Compound 2c was prepared
5
Me
5
Ti(µ-O)F] (0.872 g, 1 mmol) with AlMe
4
3
(1 mL,
2
for 20 min to give an orange yellow solution. The solution subsequently
was cooled (-10 °C) to yield 45% (0.46 g) of an orange yellow
microcrystalline solid 2c. Mp: >250 °C dec. EI-MS: m/e (%) 864
Experimental Section
All manipulations were performed under a dry nitrogen atmosphere
using standard Schlenk techniques. Solvents were dried and distilled
under nitrogen and degassed prior to use. Melting points were
+
+
1
[
M -2AlMe
NMR (C ; ppm): δ 2.08 (s, 30 H, C
and -0.81 (s, 18 H, AlMe
1:1). Anal. Calcd for C46
Found: C, 54.9; H, 7.8; F, 7.2.
Me Ti(µ-O)] [(µ-F)Al(CH
Ti(µ-O)F] (0.872 g, 1 mmol) and Al(CH
2
F] (8), 710 [M - 2AlMe
Me
). F NMR (C
Ti
2
F - F - C
), 2.10 (s, 30 H, C
; ppm): ( 95.4 and -113.1
4
: C, 54.43; H, 7.68; F, 7.48.
5
Me
5
] (100).
H
6
D
6
5
5
5
Me
5
),
1
9
6 6
D
1
19
3
determined in sealed capillaries and were not calibrated. H and
F
(
H78Al
F
2 4
O
4
NMR spectra (CDCl , C , or toluene-d solution) were recorded on
3
6
D
6
8
an AS-400 Bruker or an AM-200 Bruker spectrometer. Chemical shifts
are reported in parts per million with reference to external TMS or
CFCl . Mass spectra were obtained on a Finnigan MAT 8230 and a
3
Varian MAT CH5 spectrometer. Elemental analyses were carried out
by the Analytical Laboratory of the Institute of Inorganic Chemistry at
G o¨ ttingen.
[C
5
5
F
4 3
2 3
Ph) ] (3a). A mixture of [C
5 5
Me -
4
2
Ph) (0.3 g, 1 mmol) in
3
toluene (20 mL) was stirred at room temperature overnight. The
reaction mixture obtained was filtered and subsequently cooled (-10
°
C) to yield 40% (0.47 g) of yellow crystals 3a. Mp: 175-178 °C.
+
1
EI-MS: m/e (%) 872 [M - Al(CH
NMR (CDCl ; ppm): δ 7.18-6.85 (m, 15 H, C
Me ), 2.09 (s, 30 H, C Me ), 2.08 (s, 15 H, C Me
H, CH ). F NMR (CDCl ; ppm): δ 90.69, 87.25, and -133.95 (2:
:1). Anal. Calcd for C61 Ti : C, 62.46; H, 6.91; F, 6.48.
Found: C, 62.5; H, 6.9; F, 6.8.
Me Ti(µ-O)] [(µ-F)AlEt
µ-O)F] (0.872 g, 1 mmol) in toluene (15 mL) was added AlEt
2
Ph)
3
] (10), 91 [CH
), 2.10 (s, 15 H,
), and 1.70 (s, 6
2
Ph] (100). H
19a
5 4 4 6 5 5
) Ti O Me -
,19b [C
The starting materials [C
5
Me
SnF, and Al(CH
the literature methods. Me SiCl, AlMe
from Aldrich Chemical Co. and used as received.
Me Ti Cl (1a). The known organotitanoxane chloride 1a
was prepared in a better yield using the following modified procedure.
A mixture of (C Me Ti (4.14 g, 5 mmol) and TiCl ‚2THF (0.835
5
TiOCl]
3
,
(C
5
Me
were prepared according to
, and AlEt were purchased
3
6 5
H
5
a
5a
20
Ti(µ-O)F]
4
,
Me
3
2 3
Ph)
C
5
5
5
5
5
5
3
3
3
19
2
3
1
H81AlF O
4 4
4
(C
5
5
)
4
4
O
5
2
1
4
[C
5
5
4
F
3
3
] (3b). To a solution of [C
5
Me
5
Ti-
(1
5
5
)
4
4
O
6
4
(
4
3
g, 2.5 mmol) in toluene (40 mL) was stirred at room temperature
overnight. The reaction mixture was subsequently filtered and dried
in vacuo to afford a yellow solid. The yellow solid obtained was
washed with n-hexane to yield 82% (3.62 g) of analytically pure 1a.
mL, 1.0 M in n-hexane) through a syringe at 0 °C. The resulting pale
orange yellow solution was left at room temperature overnight and
subsequently cooled (-10 °C) to yield 30% (0.30 g) of analytically
+
pure 3b. Mp: 240-243 °C. EI-MS: m/e (%) 872 [M - AlEt
3
] (6),
; ppm): δ
), 2.07 (s, 15 H, C Me ),
). F NMR
+
+
Mp: 350-353 °C. EI-MS: m/e (%) 882 [M ] (8), 747 [M -C
5
Me
100). H NMR and analytical data are similar to those previously
reported.
Me
SnF (1.46 g, 8 mmol) in toluene (40 mL) was stirred at room
5
]
+
1
4
2
1
97 [M - AlEt
.11 (s, 15 H, C Me
.70-1.69 (tr, 9 H, CH
3
- C
), 2.09 (s, 30 H, C
), and 0.43-0.55 (qt, 6 H, CH
5
Me
5
TiF
3
] (100). H NMR (C
6 6
D
1
(
5
5
5
Me
5
5
5
19
3
2
(C
5
5
)
4
Ti
4
O
5
F
2
(1b). A suspension of 1a (3.53 g, 4 mmol) and
(C D ; ppm): δ 96.50, 92.81, and -121.35 (2:1:1). Anal. Calcd for
C H AlF O Ti : C, 55.98; H, 7.60; F, 7.71. Found: C, 56.0; H, 7.4;
46 75 4 4 4
6
6
Me
3
temperature overnight and filtered. The volatiles were removed under
reduced pressure to afford a yellow solid. The product was purified
by recrystallization from toluene to yield 85% (2.89 g). Mp: >350
F, 7.0.
[C Me Ti(µ-O)Et] (4). To a solution of [C Me Ti(µ-O)F] (0.87
5
5
4
5
5
4
g, 1 mmol) in toluene (15 mL) was added AlEt (4 mL, 1.0 M in
3
+
+
1
°
C dec. EI-MS: m/e (%) 850 [M ] (6), 715 [M -C
5
Me
; ppm): δ 2.00 and 1.94 (1:1). F NMR (CDCl
Ti : C, 56.47; H, 7.06; F, 4.47.
5
] (100). H
n-hexane) through a syringe at -10 °C. The yellow color of the
reaction mixture changed to bright-red soon after the addition was
completed and then turned to brown yellow with stirring at room
temperature overnight. After removal of the volatiles and recrystalli-
zation of the residue from n-hexane, yellow pale crystals of 4 in 40%
(0.36 g) yield were obtained. Mp: > 260 °C dec. EI-MS: m/e (%)
1
9
NMR (CDCl
δ 54.5. Anal. Calcd for C40
3
3
; ppm):
H F
60 2
O
5
4
Found: C, 56.2; H, 7.1; F, 4.7.
(C
5
Me
5
)
4
Ti
4
O
5
Me
2
(1c). 1c was prepared by reacting 1b (0.85 g,
1
mmol) with AlMe
3
(1 mL, 2 mmol) in toluene (15 mL) at 0 °C; a
+
+
1
bright-red solution formed soon after mixing and turned into orange
yellow after 1 h of stirring at room temperature. The solution was
883 [M - Et] (8), 823 [M - Et - 2C
ppm): δ 1.98 (60 H, C Me ), 1.82-1.71 (tr, 12 H, CH
1.28 (qt, 8 H, CH ). Anal. Calcd for C48 Ti : C, 63.16; H, 8.77.
Found: C, 62.9; H, 8.7.
Fluorine(oxygen)-Chlorine Exchange Reaction of [C
O)F] , 1a, 1b, [C Me Ti(µ-O)Cl] and (C Me Ti Using Me
2
H
6
] (100). H NMR (C
6 6
D ;
5
5
3
), and 1.39-
concentrated to 5 mL and cooled (-10 °C) to yield 80% (0.67 g) of
2
H
80
O
4
4
1
1
c. The H NMR and MS spectra are identical to those described in
1
3
the literature.
5
Me
5
Ti(µ-
3
SiCl.
[C
5
Me
5
3 4 5 5
Ti(µ-O)(µ-F)AlMe ] (2a). To a solution of [C Me Ti(µ-
4
5
5
3
5
5
)
4
4
O
6
All reactions were carried out following the same procedure and under
the same conditions. A representative example is the following: To a
solution of 1b (0.85 g, 1 mmol) in toluene (15 mL) was added Me -
3
SiCl (0.22 g, 2 mmol) at room temperature. The reaction mixture was
stirred for 3 h, and the volatiles were removed under reduced pressure
to give a yellow solid. The yellow solid was washed with n-hexane
O)F]
AlMe
4
(0.87 g, 1 mmol) in toluene (15 mL) with stirring was added
3
(2 mL, 2.0 M in toluene) at once using a syringe at -20 °C. A
bright-red solution formed immediately. The reaction mixture was
stirred for 5 min and subsequently cooled (-20 °C) to yield 52% (0.6
g) of red crystals of 2a. The solution of compound 2a is unstable and
(
10 mL) to yield 95% (0.83 g) of analytically pure 1a . Furthermore,
(
19) (a) Carofiglio, T.; Floriani, C.; Sgamellotti, A.; Rosi, M.; Chiesi-Villa,
A.; Rizzoli, C. J. Chem. Soc., Dalton Trans. 1992, 1081. (b) Palacios,
F.; Royo, P.; Serrano, R.; Balcazar, J. L.; Fonseca, I.; Florencio, F. J.
Organomet. Chem. 1989, 375, 51.
treating 1a or 1b (1 mmol) in toluene (15 mL) with an excess of Me
SiCl (10 mmol) by stirring at room temperature for 3 h resulted in a
red reaction mixture. The volatiles were removed subsequently to yield
3
-
(20) Eisch, J. J.; Biedermann, J.-M. J. Organomet. Chem. 1971, 30, 167.
5 5 3
95% of C Me TiCl .
Yu, Peihua
