L.I. Strunkina et al. / Journal of Organometallic Chemistry 691 (2006) 557–565
563
dried over sodium tetraethylaluminate, distilled and stored
under Ar. GLC–MS analyses were performed on a VG
7070E instrument (ionization energy 70 eV, temperature
of ion source 150 ꢀC) using the capillary SE-54 column.
Ethylene and propylene were determined by GLC on a
Chromatograph 3700-00 instrument with a flame ioniza-
tion detector and the capillary OV-101 column (30 ꢀC).
The mass spectra of 3 and 4 were measured on a AMD
402 instrument (70 eV). The 1H, 13C and 11B NMR spectra
the GLC–MS method. The analysis revealed the presence
of hexachloroethane in the solution.
4.2. Reaction of complex 1 with 1,2-dibromoethane
A mixture of 0.34 g (0.46 mmol) of 1 Æ 0.5PhCH3 and
12 ml of dry 1,2-dibromoethane was vigorously shaken
for several minutes at 20 ꢀC under Ar and the resulting
dark reddish-brown solution was allowed to stand at the
same temperature in an Ar atmosphere. After 20 h, the
solution was concentrated to ca. 8 ml and kept overnight.
In the next day, the precipitated dark brown crystals of
complex 4 were separated by decanting and dried at
20 ꢀC for 2 h in vacuum. After drying, the complex con-
tained half a mole of 1,2-dibromoethane per one mole of
4. The yield of 4 Æ 0.5C2H4Br2 is 0.26 g (65%), m.p. 192–
194 ꢀC (dec.) under Ar. Anal. Calc. for C28H9TiB-
BrF15 Æ 0.5C2H4Br2: C, 40.37; H, 1.28. Found: C, 40.39;
were recorded on a Bruker ARX-400 spectrometer, the 19
F
NMR spectra were registered on a AC-250 spectrometer.
1H and 13C chemical shifts are given relative to TMS and
are referenced to signals of the [D6]benzene used
(dH = 7.16 ppm, dC = 128.0 ppm); 19F chemical shifts are
given relative to CFCl3; 11B chemical shifts are given rela-
tive to BF3 Æ OEt2 in CDCl3 (N(11B) = 32.083971 MHz).
The assignment of the NMR signals was conducted with
the help of DEPT and shift correlation experiments. The
molecular masses of poly-e-CL were measured by the
GPC method on a Hewlett–Packard liquid chromatograph
1
H, 1.11%. H NMR (C6D6, 297 K, d, ppm): 5.42 (dt, 1H,
C5H4(3)), 5.67 (s, 5H, C5H5), 5.80 (dt,3J = 2.8 Hz,
4J = 2.2 Hz, 1H, C5H4(4)), 6.91 (br, 1H, C5H4(5)), 7.08
(br, 1H, C5H4(2)). 13C NMR (C6D6, 297 K, d, ppm):
4
3
˚
˚
˚
1090 HP (SDV column 10 A + 10 A + 100 A (Polymer
Standard Service), eluent THF) and were corrected by
the universal calibration relative to polystyrene standards.
117.2 (C5H4(3)), 122.4 (C5H5), 125.8 (C5H4(2)), 132.9
1
(C5H4(4)), 136.1 (C5H4(5)), 137.5 (meta-C6F5, JC,F
=
1
4.1. Reaction of complex 1 with CCl4
252 Hz), 139.5 (para-C6F5, JC,F = 251 Hz), 149.0 (ortho-
C6F5, JC,F = 234 Hz); signals of the C5H4(1) and ipso-
1
An amount of 11.4 ml of dry CCl4 was added to 0.39 g
(0.53 mmol) of 1 Æ 0.5PhCH3 and the resulting mixture
was vigorously shaken for several minutes at room tem-
perature in an Ar atmosphere. In the course of the reac-
tion, dark blue colour of starting 1 Æ 0.5PhCH3 rapidly
disappeared and a dark reddish-brown solution was
formed. After 1 day, the solution was concentrated to
ca. 8 ml and allowed to stand at 20 ꢀC under Ar. After
18 h, the precipitated dark brown crystals of complex 3
were separated from the mother liquor by decanting,
washed with dry CCl4 and dried at 20 ꢀC in vacuum. De-
spite drying, the obtained complex contained half a mole
of CCl4 per one mole of 3. The yield of 3 Æ 0.5CCl4 is 0.3 g
(71%), m.p. 186–187 ꢀC (dec.) under Ar. Anal. Calc. for
C28H9TiBClF15 Æ 0.5CCl4: C, 42.71; H, 1.13. Found: C,
C6F5 carbon atoms were not observed. 11B NMR (C6D6,
297 K, d, ppm): ꢁ16.7 (half width 21 Hz). 19F NMR
(C6D6, 297 K, d, ppm): ꢁ160.5 (t, 20 Hz, meta-C6F5),
ꢁ155.7 (t, 21 Hz, para-C6F5), ꢁ136.7 (br, ortho-C6F5).
MS (m/z): 768 [M+], 689 [(M ꢁ Br)+], 703 [(M ꢁ Cp)+],
576 [(C5H4B(C6F5)3)+], 512 [(B(C6F5)3)+]. The analysis of
organic products of the reaction by GLC showed the pres-
ence of ethylene in the gaseous phase and in the reaction
solution.
4.3. Reaction of complex 1 with n-propyl iodide
A mixture of 0.24 g (0.33 mmol) of 1 Æ 0.5PhCH3 and
5 ml of n-propyl iodide was vigorously shaken for several
minutes at room temperature under Ar. During the course
of the reaction, the rapid formation of a dark brown solu-
tion was observed, and small amounts of fine dark crystals
of Cp2TiI2 appeared on the walls and the bottom of the
Schlenk tube. After 24 h, the solution was concentrated
to 2–3 ml and allowed to stand at 20 ꢀC in an Ar atmo-
sphere. After 3 days, the resulting dark red crystals of
Cp2TiI2 were separated by decanting and dried at 20 ꢀC
in vacuum. The yield of Cp2TiI2 is 0.1 g (70%), m.p. 317–
319 ꢀC (dec.) under Ar (lit. m.p. 317–319 ꢀC [32]). Anal.
Calc. for C10H10TiI2: C, 27.81; H, 2.33. Found: C, 28.08;
H, 2.15%. The decanted solution was then evaporated in
vacuum to dryness at 20 ꢀC and the residue was carefully
extracted with dry n-hexane (3 · 20 ml). The subsequent
evaporation of the resulting n-hexane extract and drying
in vacuum at 20 ꢀC gave a white powder of crude
B(C6F5)3 with m.p. 129–135 ꢀC (dec.) under Ar (lit. m.p.
1
42.10; H, 1.10%. H NMR (C6D6, 297 K, d, ppm): 5.58
(m, 1H, C5H4(3)), 5.60 (m, 1H, C5H4(4)), 5.62 (s, 5H,
C5H5), 6.69 (br, 1H, C5H4(5)), 7.02 (br, 1H, C5H4(2)).
13C NMR (C6D6, 297 K, d, ppm): 117.9 (C5H4(3)),
122.6 (C5H5), 125.5 (C5H4(2)), 133.4 (C5H4(4)), 136.6
1
(C5H4(5)), 137.5 (meta-C6F5, JC,F
= 251 Hz), 139.5
1
1
(para-C6F5, JC,F = 251 Hz), 149.0 (ortho-C6F5, JC,F
=
234 Hz); signals of the C5H4(1) and ipso-C6F5 carbon
atoms were not observed. 11B NMR (C6D6, 297 K, d,
ppm): ꢁ16.5 (half width 21 Hz). 19F NMR (C6D6,
297 K, d, ppm): ꢁ160.6 (t, 23 Hz, meta-C6F5), ꢁ155.8
(t, 21 Hz, para-C6F5), ꢁ136.8 (br, ortho-C6F5). MS
(m/z): 724 [M+], 689 [(M ꢁ Cl)+], 658 [(M ꢁ CpH)+],
576 [(C5H4B(C6F5)3)+], 512 [(B(C6F5)3)+]. For identifica-
tion of organic products of the reaction, the solution ob-
tained after separation of crystals of 3 was analyzed by
Strunkina
