Monosulfonated Triphenylphosphane (TPPMS) Derived Ligand
UPDATES
ed), 7.84 (broad d, J ꢀ 7.6 Hz, 1H, sulfonated), 7.87 (broad
Sodium 5-[Bis(4-trifluoromethylphenyl)phosphanyl]-
2-methoxybenzenesulfonate (6)
d,
J
ꢀ
7.5 Hz, 1H, sulfonated) ppm; 13C{1H}-NMR
(CD3OD): d=127.45 (s, C4{sulfonated}), 129.57 (d, JPC
=
6.1 Hz, sulfonated), 129.74 (d, 3JPC =7.2 Hz, meta-phenyl),
130.12 (s, para-phenyl), 131.97 (d, JPC =22.9 Hz, sulfonated),
Fuming sulfuric acid (2.5 mL, 20% of free SO3) was trans-
ferred in a round-bottom flask under argon. The flask was
placed in a salt/ice bath, and (4-anisyl)bis(4-trifluoromethyl-
phenyl)phosphane (5, 1 g, 2.33 mmol) was added to the
fuming sulfuric acid in small portions. The bath was re-
moved and the reaction mixture was stirred for one hour.
The flask was placed in an ice/salt bath again and crushed
ice (~10 g) was added over a 30 min period. In the course of
the procedure the phosphonium salt precipitated as a sticky
material. Sufficient blending was maintained by shaking the
flask gently. The acidic reaction mixture was carefully neu-
134.80 (d, 2JPC =19.1 Hz, ortho-phenyl), 136.27 (d, JPC
=
1
18.2 Hz, sulfonated), 137.99 (d, JPC =10.8 Hz, ipso-phenyl),
139.68 (d, JPC =14.6 Hz, sulfonated), 146.59 (d, JPC =6.2 Hz,
sulfonated); 31P{1H}-NMR (CD3OD): d=À5.0 (s) ppm;
anal. calcd. for C18H14NaO4PS·H2O (Mr =382.28): P 8.10, S
8.37, Na 6.01; found: P 8.07, S 8.64, Na 5.94. Degree of sul-
fonation: S/P=1.03.
tralized with aqueous NaOH solution (3.95 g NaOH in Rh(phosphane)2(CO)Cl Complexes
30 mL water). The pH of the suspension was set to ~7.
(Controlled by special pH paper.) The aqueous suspension
was transferred in a 500 mL flask under argon, and the
water was removed under vacuum. (Due to intensive foam
formation, the use of a smaller flask is not advisable.) The
white residue was extracted with methanol (250 mL).
Water (10 mL) was added to the methanol solution, then
the solvent was removed. The product is a white solid.
Yield: 1.20 g (94%); 1H NMR (CD3OD): d=3.94 (s, 3H,
[Phosphane=PPh3, PPh2(p-C6H4OCH3),
P(p-C6H4CF3)2(p-C6H4OCH3)]
Phosphanes (0.168 mmol) dissolved in CH3CN (2 mL) were
added to [Rh(CO)2Cl]2 (15.6 mg, 0.04 mmol) dissolved in
CH3CN (1 mL). The Schlenk flask of the phosphanes was
rinsed with further 1 mL of CH3CN. The reaction mixtures
were stirred for 60–120 min. The solvent was removed under
vacuum. The isolated solids were washed with Et2O and
dried under vacuum for 15 min at room temperature. (The
last operation should not be carried out in the case of 5,
since the complex is considerably soluble in Et2O.) Each
complex was also prepared in a similar manner using
CH2Cl2 as solvent instead of CH3CN. 31P{1H}-NMR (CDCl3)
spectra were recorded of the products prepared in CH3CN.
3
4
OCH3), 7.17 (dd, JHH =8.4 Hz, JPH =0.7 Hz, 1H, C5{sulfo-
nated}-H), 7.41–7.51 (m, 5H, C2{p-C6H4CF3}-H, C6{sulfo-
3
nated}-H), 7.66 (broad pseudo d, JHH ꢀ 8 Hz, 4H, C3{p-
C6H4CF3}-H), 7.96 (dd, 3JPH =7.7 Hz, 4JHH =2.4 Hz, 1H,
C2{sulfonated}-H); 13C{1H}-NMR (CD3OD): d=56.49 (s,
OCH3), 113.77 (d, 3JPC =9.7 Hz, C3{p-C6H4OCH3}), 125.32
1
31P{1H}-NMR data of the complexes are as follows. Rh-
(q, JFC =271.3 Hz, CF3), 125.91 (d, JPC =9.7 Hz, sulfonated),
2
126.28 (m, 3JFC =3.6 Hz, C3{p-C6H4CF3}), 131.70 (q, JFC
=
1
A
U
C6H4OCH3)]2(CO)Cl: d=27.6 ppm (d, 1JRhP =127 Hz);
Rh[P(p-C6H4CF3)2(p-C6H4OCH3)]2(CO)Cl: d=30.5 ppm (d,
1JRhP =128 Hz). IR (KBr pellets) spectra were recorded of
each batch using three different FT-IR spectrometers. 6–10
spectra were recorded of each complex. Depending on the
conditions of the syntheses and the measurements, the nCO
32.7 Hz, C4{p-C6H4CF3}), 133.67 (d, JPC =10.9 Hz, sulfonat-
ed), 134.60 (d, 2JPC =19.4 Hz, C2{p-C6H4CF3}), 135.61 (d,
2JPC =23.0 Hz, C2{sulfonated}), 139.54 (d, 2JPC =24.2 Hz,
C2{sulfonated}), 143.68 (broad d, 1JPC =14.5 Hz, C1{p-
C6H4CF3}), 159.53 (s, C4{sulfonated}); 31P{1H}-NMR
(CD3OD): d=À2.4 (s) ppm; MS (ESI-): m/z=507.1
[MÀNa+]; MS (ESI+): m/z=508.9 [MÀNa+ + 2H+]+; anal.
calcd. for C21H14F6NaO4P·H2O (Mr =548.37): P 5.64, S 5.84,
Na 4.19; found: P 5.58, S 5.81, Na 3.89. Degree of sulfona-
tion: S/P=1.01.
values fell in the following ranges: RhACHTREUNG
1964.8–1966.2 cmÀ1
1963.2–1965.1 cmÀ1
;
;
RhACHTREUNG
Rh[P(p-C6H4CF3)2(p-C6H4OCH3)]2-
(CO)Cl: n=1982.3–1984.0 cmÀ1. The average (rounded) nCO
values are summarized in Table 1.
Sodium (Diphenylphosphanyl)benzenesulfonate (1)
Phosphane Selenides [Phosphane=PPh3,
PPh2(p-C6H4OCH3), 5, 6]
Triphenylphosphane (20.0 g, 76.3 mmol) was slowly added to
fuming sulfuric acid (50 mL, 20% of free SO3). When the
phosphane had completely dissolved, the homogenous reac-
tion mixture was heated at 97–988Cfor 75 min. The reaction
mixture was allowed to cool to room temperature, and then
it was poured on crushed ice (400 g). The pH of the milky
reaction mixture was set to ~4 using 50% NaOH solution.
The precipitate was filtered and recrystallized twice from
water [1) 550 mL of warm water, then refrigerator over-
night. 2) 60 mL of hot water.] The second recrystallization
yielded 7.0 g analytically pure TPPMS monohydrate. In a re-
frigerator further 3.5 g of pure product crystallized from the
mother liquor in two days. Total yield: 10.5 g (36%);
1H NMR (CD3OD): d=7.24–7.36 (m, 11H, Ph and 1H sul-
fonated), 7.40 (broad pseudo t, J ꢀ 7–8 Hz, 1H, sulfonat-
The selenides were prepared by the reaction of the phos-
phanes and elemental selenium in refluxing CHCl3 (EtOH
in the case of 6) according to a literature method.[16] 31P{1H}-
NMR (CDCl3) spectra were recorded in CDCl3. 31P{1H}-
NMR data of the complexes are as follows: Se=PPh3: d=
37.3 ppm (d, 1JSeÀP =729 Hz); Se=PPh2(p-C6H4OCH3): d=
1
36.1 ppm (d, JSeÀP =723 Hz); selenide of 5: d=35.4 ppm (d,
1JSeÀP =747 Hz); selenide of 6: d=35.3 ppm (d, JSeÀP
=
1
754 Hz).
Adv. Synth. Catal. 2006, 348, 1306 – 1310
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1309