E. Lindner, T. Salesch / Journal of Organometallic Chemistry 628 (2001) 151–154
153
3. Experimental
3 days. Distillation under vacuum affords 3(T0) as a
colorless, airstable oil that is sensitive to moisture.
1
Yield 36.4 g (91.3%), b.p. 135°C (0.1 mbar). H-NMR
3.1. General remarks
(CDCl3): l=7.28 (d, 3JHH=8.17 Hz, 2H, 2,6-benzene),
3
6.95 (d, JHH=8.16 Hz, 2H, 3,5-benzene), 4.10 (hept,
If not stated otherwise, all experiments were carried
out under dry argon. THF was distilled from sodium
benzophenone ketyl. MeOH was dried and distilled
from magnesium and CH2Cl2 from CaH2. RhCl3·xH2O
was a gift from Degussa AG. [m-ClRh(CO)2]2 [14] and
the starting compound 1 [15] were prepared according
to the literature methods. HSiCl3 and Ph2PCl were
purchased from Acros and distilled prior to use. Triiso-
propyl orthoformate and all other chemicals were pur-
chased from Fluka and Merck/Germany, respectively,
and used without further purfication. Elemental analy-
ses were carried out on an Elementar Vario EL ana-
lyzer. High-resolution 1H-, 13C{1H}-, 29Si{1H}-, and
31P{1H}-NMR spectra were recorded on a Bruker
DRX 250 spectrometer at 296 K. Frequencies are as
3
3JHH=6.28 Hz, 3H, OꢀCH), 2.46 (t, JHH=7.85 Hz,
2H, BrꢀC6H4ꢀCH2), 1.54 (m, 2H, C6H4ꢀCH2ꢀCH2),
3
1.38 (m, 2H, CH2ꢀCH2ꢀSi(Oi-Pr)3), 1.09 (d, JHH
=
6.28 Hz, 18H CH3), 0.52 (m, 2H, CH2ꢀSi(Oi-Pr)3) —
13C{1H}-NMR (CDCl3): l=142.1 (s, CꢀCH2), 131.6
(s, CHꢀCBr), 130.6 (s, CHꢀCꢀCH2), 119.6 (s, CBr),
65.2 (s, CHꢀO), 35.3 (s, C6H4ꢀCH2), 35.1 (s,
3
C6H4ꢀCH2ꢀCH2), 25.7 (d, JHH=6.29 Hz, 18H, CH3),
23.0 (s, CH2ꢀCH2ꢀSi(Oi-Pr)3), 12.2 (s, CH2ꢀSi(Oi-Pr)3)
—
29Si{1H}-NMR (CDCl3): l=−48.8 (s). EIMS; m/z:
418 [M]+. Anal. Found: C, 54.61; H, 7.90. Calc. for
C19H33BrO3Si: C, 54.67; H, 7.97%.
1
follows: H-NMR — 250.12 MHz; 13C {1H}-NMR —
3.4. [p-Butyl(4-triiosopropoxysilyl)phenyl]diphenyl-
phosphine [4(T0)]
62.90 MHz; 29Si {1H}-NMR — 49.69 MHz; 31P{1H}-
1
NMR — 101.25 MHz. The chemical shifts in the H-,
13C{1H}-, 29Si{1H}-, and 31P{1H}-NMR spectra were
measured relative to partially deuterated solvent peaks
which are reported relative to TMS. Mass spectra:
EIMS; Finnigan TSQ 70 (200°C). FABMS; Finnigan
711A (8 kV), modified by AMD and reported as mass/
charge (m/z).
Magnesium (1.20 g, 50.0 mmol) and 50 ml of THF
were placed in a three-necked flask equipped with a
magnetic stirrer, a condenser, and a dropping funnel.
After activation of the magnesium by some pieces of
iodine, a solution of 3(T0) (20.87 g, 50.0 mmol) in 50 ml
of THF was added dropwise. The reaction mixture was
refluxed for 3 h, decanted from excess magnesium and
cooled to −20°C. Subsequently dichlorophenylphos-
phine (10.14 g, 45.0 mmol) was added to the Grignard
solution. The mixture was stirred for 12 h at r.t. THF
was removed and n-pentane (300 ml) was added. After
filtration and removal of the solvent under vacuum, an
oily product was obtained which is sensitive to moisture
3.2. p-Bromo[4-(trichlorosilyl)butyl]benzene (2)
A mixture of p-bromobutenylbenzene (1) (27.6 g,
130.7 mmol), trichlorosilane (26.6 g, 196.1 mmol) and
hexachloroplatinic(IV) acid (15 mg, 0.029 mmol) in 25
ml of THF was stirred for 1 day at room temperature
(r.t.). Distillation under vacuum affords 2 as a colorless,
airstable oil which is sensitive to moisture. Yield 33.1 g
(73.1%), b.p. 145°C (0.3 mbar). 1H-NMR (CDCl3):
1
and air. Yield 17.5 g (63.0%). H-NMR (CDCl3): l=
7.24–7.08 (m, 14H, phenyl+phenylene), 4.10 (hept,
3
3JHH=6.27 Hz, 3H, OꢀCH), 2.53 (t, JHH=7.85 Hz,
3
l=7.31 (d, JHH=8.16 Hz, 2H, 2,6-benzene), 6.96 (d,
2H, C6H4ꢀCH2), 1.58 (m, 2H, C6H4ꢀCH2ꢀCH2), 1.37
3
3JHH=8.16 Hz, 2H, 3,5-benzene), 2.51 (t, JHH=6.91
3
(m, 2H, CH2ꢀCH2ꢀSi(Oi-Pr)3), 1.09 (d, JHH=6.28 Hz,
18H, CH3), 0.54 (m, 2H, CH2ꢀSi(Oi-Pr)3) — 13C{1H}-
NMR (CDCl3): l=143.7 (s, para-C-phenylene), 137.5
(d, 1JPC=10.6 Hz, ipso-C-phenyl), 133.8 (d, 2JPC=20.2
Hz, ortho-C-phenylene), 133.7 (m, ipso-phenylene),
133.5 (d, 2JPC=19.1 Hz, ortho-C-phenyl), 128.7 (d,
Hz, 2H, BrꢀC6H4ꢀCH2), 1.56 (m, 4H, CH2ꢀ
CH2ꢀCH2ꢀCH2), 1.34 (m, 2H, CH2ꢀSiCl3) — 13C{1H}-
NMR (CDCl3): l=141.1 (s, CꢀCH2), 131.8 (s,
CHꢀCBr), 130.5 (s, CHꢀCꢀCH2), 120.0 (s, CBr), 35.1
(s, C6H4ꢀCH2), 33.8 (s, C6H4ꢀCH2ꢀCH2), 24.5 (s,
CH2ꢀCH2ꢀSiCl3), 22.3 (s, CH2ꢀSiCl3).
1
3JPC=7.4 Hz, meta-C-phenylene), 128.5 (d, JPC=9.4
3
Hz, ipso-C-phenylene), 128.3 (d, JPC=6.7 Hz, ortho-
C-phenyl), 64.8 (s, CHꢀO), 35.3 (s, C6H4ꢀCH2), 34.7 (s,
C6H4ꢀCH2ꢀCH2), 25.5 (CH3), 22.6 (s, CH2ꢀCH2ꢀSi(Oi-
3.3. p-Bromo[4-(triisopropoxysilyl)butenyl]benzene
[3(T0)]
Pr)3), 11.8 (s, CH2ꢀSi(Oi-Pr)3)
—
29Si{1H}-NMR
(CDCl3): l= −48.6 (s) — 31P{1H}-NMR (CDCl3):
l= −4.98 (s). EIMS; m/z: 522 [M]+. Anal. Found: C,
70.61; H, 8.23. Calc. for C31H43O3PSi: C, 71.23; H,
8.29%.
Under ambient temperature, triisopropyl orthofor-
mate (67.4 g, 354.0 mmol) was added dropwise to
p-bromo[4-(trichlorosilyl)butyl]benzene (2) (33.1 g, 95.5
mmol). After the addition, the solution was stirred for