G. Francio` et al. / Journal of Organometallic Chemistry 621 (2001) 130–142
141
4.8. Synthesis of (R)-2%-{bis-[3-(3,3,4,4,5,5,6,6,7,7,-
8,8,8-tridecafluoro-octyl)-phenyl]-phosphanyl}-[1,1%]-
binaphthalenyl-2-ol (9)
128.28 (s, arom CH), 128.21 (s, arom CH), 127.41 (d,
P(2)C=2.0 Hz, arom CH), 127.38 (s, arom CH),
J
127.27 (s, arom CH), 127.24 (s, arom CH), 127.16 (s,
arom CH), 126.69 (s, arom CH), 126.59 (s, arom CH),
126.44 (s, arom CH), 126.34 (s, arom CH), 125.29 (s,
arom CH), 125.01 (s, arom CH), 124.88 (s, arom CH),
123.35 (d, JP(1)C=1.7 Hz, arom C), 121.98 (s, arom
CH), 121.85 (s, arom CH), 120.98 (d, JP(1)C=8.6 Hz,
Trichlorosilane (1.92 ml, 0.014 mol) and triethy-
lamine (2.8 ml) was added to a solution of 8 (2.03 g,
0.02 mol) in toluene (40 ml) at 0°C. The reaction
mixture was heated at 100°C for 12 h. After cooling to
r.t., the reaction mixture was quenched with degassed 2
N NaOH (1 ml). The organic phase was filtered
through a path of Celite and MgSO4, and then concen-
trated under reduced pressure to give 9 as a white solid.
Yield: 61%.
arom CH), 120.55–106.75 (m, CFx), 32.51 (t, JFC
=
22.0 Hz, CH2CH2CF2), 32.31 (t, FC=21.9 Hz,
J
CH2CH2CF2), 26.27 (s, CH2CH2CF2), 26.12 (s,
CH2CH2CF2). 19F-{1H}-NMR (282.4 MHz, CDCl3):
l= −81.3 (m, 6F, CF3), −114.6 (m, 4F, CF2), −
122.1 (m, 4F, CF2), −123.1 (m, 4F, CF2), −123.5 (m,
2F, CF2), −123.7 (m, 2F, CF2), −126.4 (m, 4F, CF2).
LCMS (ESIpos): 1461 [M+H]. [h]2D0= +177° (ca. 1.0,
toluene).
31P-{1H}-NMR (C6D6): l= −12.7 (s). 1H-NMR
(C6D6): l=8.00–7.28 (m, 10H, Ar–H), 7.22–6.60 (m,
10H, Ar–H), 2.80–2.63 (m, 2H, CH2), 2.57–2.42 (m,
2H, CH2), 2.29–1.80 (m, 4H, CH2). LCMS (ESIpos):
1147 [M+H].
4.10. Synthesis of the complex [Rh(10)(acac)] (11)
4.9. Synthesis of 4-(2%-{bis-[3-(3,3,4,4,5,5,-
6,6,7,7,8,8,8-tridecafluoro-octyl)-phenyl]-phosphanyl}-
[1,1%]-(R)-binaphthalenyl-2-yloxy)-3,5-
A pre-cooled solution of the ligand 10 (146 mg, 0.1
mmol) in THF (10 ml) was added to a solution of
[Rh(acac)(CO)2] (25.8 mg, 0.1 mmol) in THF (10 ml) at
−78°C. After 30 min at −78°C, the reaction mixture
was slowly allowed to warm to r.t. and then stirred for
further 60 min. The reaction mixture was concentrated
to a volume of about 2 ml and pentane was added (20
ml) to form a bright-yellow precipitate that was col-
lected and washed with pentane (10 ml). Yield 98%.
31P-{1H}-NMR (C6D6): l=161.9 (dd, JPP%=84,
dioxa-4-phospha-cyclohepta[2,1-a;3,4-a%]-(S)-
dinaphthalene, 3-H2F6-(R,S)-BINAPHOS (10)
A solution of 9 (2.0 g, 1.74 mmol) and triethylamine
(1.2 ml, 8.6 mmol) in toluene (20 ml) was added
dropwise at 0°C to a solution of (S)-4-chloro-3,5-dioxa-
4-phospha-cyclohepta[2,1-a;3,4-a%]dinaphthalene (0.611
g, 1.74 mmol) in toluene (10 ml). The reaction mixture
was stirred overnight at r.t., filtered off, and concen-
trated under reduced pressure. The residue was ex-
tracted with pentane to obtain the pure title compound.
Yield: 99% (white solid).
J
RhP=330 Hz), 49.6 (dd, JRhP%=175 Hz). 1H-NMR
(C6D6): l=8.18–6.58 (m, 32H, Ar–H), 5.26 (s, 1H,
CH), 2.81–2.63 (m, 2H, CH2), 2.52–1.68 (m, 6H, CH2),
2.18 (s, 3H, CH3), 1.34 (s, 3H, CH3). 103Rh-NMR
(C6D6): l=271.
31P-{1H}-NMR (243.0 MHz, C6D6): l=146.5 (d,
JPP%=27.8 Hz), −13.3 (d). 1H-NMR (600.2 MHz,
C6D6): l=7.88–6.38 (m, 32H, Ar–H), 2.41–2.34 (m,
4H, CH2), 1.95–1.79 (m, 4H, CH2). 13C-NMR (150.9
MHz, C6D6): l=148.20 (d, JP(1)C=4.2 Hz, arom C),
148.06 (dd, JP(1)C=8.2, JP(2)C=1.8 Hz, arom C),
Acknowledgements
This work was supported by the Max-Planck-Society,
the Deutsche Forschungsgemeinschaft (Gerhard–Hess
Award to W. L.), the Fonds der Chemischen Industrie,
and the European Community (COST-D10). We thank
Celanese GmbH, Werk Ruhrchemie, for the AAS mea-
surements and Dr Wolfgang Baumann (University of
Rostock) for the 103Rh-NMR spectra. Special thanks
are due to Professor Kyoko Nozaki for a generous
donation of BINAPHOS and a very open scientific
discussion and to Professor C.J. Elsevier for his support
in establishing high pressure NMR in our group.
147.69 (d, JP(1)C=2.5 Hz, arom C), 141.71 (d, JP(2)C
=
34.3 Hz, arom C), 139.26 (d, JP(2)C=5.6 Hz, arom C),
138.96 (s, arom C), 138.94 (d, JP(2)C=25.1 Hz, arom
C), 137.82 (d, JP(2)C=14.6 Hz, arom C), 137.01 (d,
JP(2)C=12.1 Hz, arom C), 134.91 (d, JP(2)C=31.9 Hz,
arom CH), 134.85 (d, JP(2)C=2.4 Hz, arom C), 134.28
(s, arom C), 134.06 (d, JP(2)C=7.0 Hz, arom C), 133.36
(s, arom C), 133.11 (d, JP(2)C=19.2 Hz, arom CH),
132.91 (s, arom C), 132.69 (d, JP(2)C=11.5 Hz, arom
CH), 132.04 (s, arom C), 131.92 (d, JP(2)C=17.5 Hz,
arom CH), 131.62 (s, arom C), 131.19 (s, arom C),
130.66 (s, arom CH), 130.47 (s, arom CH), 130.41 (s,
arom CH), 129.64 (s, arom CH), 129.03 (d, JP(2)C=5.5
Hz, arom CH), 128.89 (d, JP(2)C=4.7 Hz, arom CH),
128.81 (s, arom CH), 128.76 (s, arom CH), 128.61 (s,
arom CH), 128.51 (s, arom CH), 130.41 (s, arom CH),
References
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