I.D. Kostas, C.G. Screttas / Journal of Organometallic Chemistry 585 (1999) 1–6
5
4.5. o-Diphenylphosphino-[N-(2-methoxyethyl)-N-
methyl]aniline (7)
the complex 9 (92%) as an orange solid, m.p. (dec.)
197–200°C. 1H-NMR (CD2Cl2, 300 K): l 7.76–7.28
(m, 14H, Ar), 5.32 (brs, 1H, COD–CH), 3.63–3.58 (m,
1H, part of NCH2CH2O), 3.49–3.36 (m, 2H, part of
NCH2CH2O), 3.34 (s, 3H, NCH3), 3.09–3.02 (m, 1H,
part of NCH2CH2O), 2.98 (s, 3H, OCH3), 2.44 and 2.10
(2×brs, 8H, COD–CH2). 13C{1H}-NMR (CD2Cl2, 300
To a solution of 5 (6.75 g, 40.91 mmol) in ether (35
ml) under argon, was added n-butyllithium (1.6 M in
hexane, 28 ml, 44.80 mmol). The reaction mixture was
subsequently stirred at r.t. for 27 h, yielding the
organolithium 6. A solution of chlorodiphenylphos-
phine (7.8 ml, 43.45 mmol) in ether (25 ml) was then
added dropwise with ice-water bath cooling and the
mixture then stirred at r.t. overnight. The volatile mate-
rials were removed by evaporation, water was added,
the product was extracted with toluene (3×100 ml),
dried over Na2SO4, filtered and evaporated to dryness.
Purification was carried out by recrystallization from
ether, yielding 7 as a white solid (10.85 g, 76%), m.p.
70–73°C. 1H-NMR (CDCl3): l 7.35–6.76 (m, 14H,
Ar), 3.18 (t, 3J=6.5 Hz, 2H, CH2O), 3.18 (s, 3H,
K):
l
157.46–123.16 (Ar), 68.60 and 62.97
(NCH2CH2O), 59.59 (OCH3), 54.15 (NCH3), 32.19 and
28.31 (COD–CH2). 31P{1H}-NMR (CD2Cl2, 303 K): l
39.05 (d, JRhP=155.6 Hz). ESI MS: m/z (relative inten-
sity) 560 ([M−BF4]+, 100). Anal. Calc. for
C30H36BF4NOPRh (647.30): C, 55.67; H, 5.61; N, 2.16.
Found: C, 55.79; H, 5.66; N, 2.14%.
4.8. Hydroformylation
Styrene (3.4 ml, 29.67 mmol) and a 4 mM solution of
rhodium complex in dichloromethane (5 ml, 0.02
mmol) was placed under argon in an oven-dried auto-
clave, which was then closed, pressurized with syngas
(CO:H2=1:1) to 100 bar and brought to the required
temperature. After the required reaction time, the auto-
clave was cooled to r.t., the pressure was carefully
released and the solution was passed through celite and
3
OCH3), 3.02 (t, J=6.5 Hz, 2H, CH2N), 2.64 (s, 3H,
NCH3). 13C{1H}-NMR (CDCl3): l 157.36–122.21 (Ar),
71.12 (CH2O), 58.53 (OCH3), 56.31 (CH2N), 43.68
(NCH3). 31P{1H}-NMR (CDCl3): l −13.80 (s). GC–
MS (EI): m/z (relative intensity) 350 ([M+H]+, 12),
304 (49), 291 (100), 261 (7), 200 (64), 122 (9), 91 (17), 77
(13). Anal. Calc. for C22H24NOP (349.41): C, 75.62; H,
6.92; N, 4.01. Found: C, 75.55; H, 7.06; N, 4.11%.
1
analyzed by GC, GC–MS and H-NMR spectroscopy.
Conversions were determined by GC.
4.6. [Rh(COD)–4]BF4 (8)
A solution of the phosphine 4 (0.4062 g, 1.21 mmol)
in CH2Cl2 (15 ml) was added dropwise to the dark red
solution of (COD)2Rh+BF4− (0.4923 g, 1.21 mmol) in
CH2Cl2 (15 ml) with ice-water bath cooling, after which
the mixture was stirred at r.t. for 2 h. The volatile
materials were evaporated under reduced vacuum, the
residue washed with hexane and dried, yielding 8
(0.7373 g, 96%) as a pale yellow solid, m.p. 192–194°C.
IR (CHCl3): w 3684 (OH, free), 3477 (OH, H-bonded),
Acknowledgements
The investigation was supported by the National
Hellenic Research Foundation. We have pleasure in
thanking Dr B.R. Steele for helpful discussions.
References
1
1067 (BF4−). H-NMR (CD2Cl2, 303 K): l 7.81–7.29
(m, 14H, Ar), 4.20 (brs, 3H, COD–CH), 3.69 (s, 1H,
OH, exchangeable with D2O), 3.65, 3.46, 3.37–3.28 and
3.14–3.08 (4×m, 4×1H, NCH2CH2O), 3.43 (s, 3H,
NCH3), 2.56–2.48, 2.36, 2.16–2.12 and 1.97–1.91 (4×
m, 4×2H, COD–CH2). 13C{1H}-NMR (CD2Cl2, 294
[1] C.D. Frohning, C.W. Kohlpaintner, in: B. Cornils, W.A. Her-
rmann (Eds.), Hydroformylation in Applied Homogeneous
Catalysis with Organometallic Compounds, vol. 1, VCH, Wein-
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and Refs. therein.
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K):
l
157.59–123.22 (Ar), 63.96 and 58.93
(NCH2CH2O), 53.35 (NCH3), 31.52 and 29.76 (COD–
CH2). 31P{1H}-NMR (CD2Cl2, 303 K): l 40.52 (d,
J
RhP=149.6 Hz). ESI MS: m/z (relative intensity) 546
([M−BF4]+, 100). Anal. Calc. for C29H34BF4NOPRh
(633.28): C, 55.00; H, 5.41; N, 2.21. Found: C, 55.10;
H, 5.47; N, 2.20%.
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4.7. [Rh(COD)–7]BF4 (9)
[8] I.C.M. Wehman-Ooyevaar, G. Marc Kapteijn, D.M. Grove,
W.J.J. Smeets, A.L. Spek, G. van Koten, J. Chem. Soc. Dalton
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The reaction of 7 with (COD)2Rh+BF4− according
to the procedure described for the synthesis of 8 yielded