New Diphosphane Ligands Based on Bisphenol A Backbones
FULL PAPER
obtained by slow evaporation of the solvent from the NMR solu-
1
2
4 H, o-CH2, c-C6), 3.71 (s, 6 H, OCH3), 6.47 (dd, J ϭ 5.6, J ϭ
2.4 Hz, 2 H, H1), 6.72 (dd, 1J ϭ 8.8, 2J ϭ 4.8 Hz, 2 H, Ar-H2), tion. 1H NMR (400 MHz, CDCl3, 300 K, ppm): δ ϭ Ϫ0.05 (t, 6
6.99 (dd, J ϭ 8.8, J ϭ 2.4 Hz, 2 H, H3), 7.24 (m, 20 H, PPh2). H, PdCH3), 1.26 (br. s, 12 H, m,p-CH2, c-C6), 1.80 (br. s, 8 H, o-
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2
13C NMR (100 MHz, CDCl3, 300 K, ppm): δ ϭ 22.7, 26.2, 37.0,
45.2, 55.6, 109.8, 125.7, 128.2, 128.3 (d, JP,C ϭ 13.0 Hz), 128.8,
CH2, c-C6), 3.61 (s, 12 H, OCH3), 6.71 (d, J ϭ 8.0 Hz, 4 H, H3),
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7.04 (d, J ϭ 8.0 Hz, 8 H, H1, H2), 7.30 (m, 24 H, PPh2), 7.71 (br.
1
132.9, 133.7 (d, JP,C ϭ 19.8 Hz), 137.0, 140.9, 159.0 (d, JP,C
Ϫ15.2 (s). C44H42O2P2: calcd. C 79.50, H 6.37; P, 9.32; found C
79.39, H 6.39; P, 9.31
ϭ
s, 16 H, PPh2). 13C NMR (100 MHz, CDCl3, 300 K, ppm): δ ϭ
3.8, 22.8, 26.3, 37.1, 45.1, 55.5, 110.8, 119.0, 119.2, 127.5, 129.2,
130.9, 131.6, 133.3, 135.0, 140.4, 157.9. 31P{1H} NMR (162 MHz,
CDCl3, 300 K, ppm): δ ϭ 25.0 (s). C90H90Cl2O4P4Pd2: calcd. C
65.78, H 5.52; found C 65.60, H 5.46.
2,2-Bis[(3-diphenylphosphanyl-4-methoxy)phenyl]ethylbenzene (3):
Starting from C (12.4 g, 38.9 mmol), compound 3 was obtained as
a white powder using the same procedure as described for com-
pound 1. Yield 61% (16.5 g, 23.7 mmol). 1H NMR (400 MHz,
CDCl3, 300 K, ppm): δ ϭ 1.74 (s, 3 H, CCH3), 3.72 (s, 6 H, OCH3),
trans,trans-[PtCl2-2]2, Complex 7: PtCl2 (170.3 mg, 640.5 µmol) was
heated to reflux in acetonitrile (10 mL) until the solid had com-
pletely dissolved. Ligand 2 (425.8 mg, 640.5 µmol) was added and
the mixture stirred under reflux for about 10 h. After cooling to
room temp., the solvent was evaporated in vacuo to leave a yellow
powder. Single crystals were obtained from acetone, by slow evap-
1
6.33 (dd, 1J ϭ 5.6, 2J ϭ 2.4 Hz, 2 H, H1), 6.67 (dd, J ϭ 8.8, 2J ϭ
4.8 Hz, 2 H, H2), 6.81 (m, 2 H, o-CH, Ph), 6.91 (dd, 1J ϭ 8.8, 2J ϭ
2.4 Hz, 2 H, H3), 7.07 (m, 3 H, m-,p-CH, Ph), 7.18 (m, 20 H, PPh2).
13C NMR (100 MHz, CDCl3, 300 K, ppm): δ ϭ 30.0, 51.2, 55.6,
1
oration of the solvent. H NMR (400 MHz, CDCl3, 300 K, ppm):
δ ϭ 1.23 (m, 12 H, m,p-CH2, c-C6), 1.71 (br. s, 8 H, o-CH2, c-C6),
109.3, 124.2 (d, JP,C ϭ 13.0 Hz), 125.5, 127.6, 128.2 (d, JP,C
6.8 Hz), 128.3 (d, JP,C ϭ 3.1 Hz), 130.2, 133.6 (d, JP,C ϭ 19.8 Hz),
ϭ
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3.63 (s, 12 H, OCH3), 6.67 (d, J ϭ 8.0 Hz,4 H, H1), 7.00 (br. s, 4
1
H, H2), 7.09 (d, J ϭ 8.8 Hz, 4 H, H3), 7.37 (br. m, 24 H, PPh2),
134.1, 136.7 (d, JP,C ϭ 10.7 Hz), 141.3, 149.0, 159.1 (d, JP,C
ϭ
14.5 Hz). 31P{1H} NMR (162 MHz, CDCl3, 300 K, ppm): δ ϭ
Ϫ15.3 (s). C46H40O2P2: calcd. C 80.45, H 5.87; P, 9.02; found C
80.52, H 5.76; P, 9.05.
7.73 (q, 1J ϭ 5.6 Hz, 16 H, PPh2). 31P{1H} NMR (162 MHz,
CDCl3, 300 K, ppm):
δ ϭ 15.8 (s, JPtϪP ϭ 2705 Hz).
C88H84Cl4O4P4Pt2: calcd. C 56.78, H 4.55; found C 56.65, H 4.45.
Bis[(3-diphenylphosphanyl-4-methoxy)phenyl]dimethylsilane
(4):
trans,trans-RhCl(CO)-2, Complex 8: [RhCl(CO)2]2 (170.3 mg, 640.5
µmol) and ligand 2 (425.8 mg, 640.5 µmol) were dissolved in
CH2Cl2 (10 mL) and the mixture was stirred for 2 h. Evaporation
of the solvent in vacuo yielded a yellow solid. Single crystals were
obtained by slow diffusion of CH3CN into a CH2Cl2 solution of
Starting from D (3.00 g, 0.011 mol), compound 4 was obtained as
a white powder using the same procedure as described for com-
pound 1. Yield 65% (4.58 g, 7.20 mmol). 1H NMR (400 MHz,
CDCl3, 300 K, ppm): δ ϭ 0.09 [s, 6 H, Si(CH3)], 3.75 (s, 6 H,
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OCH3), 6.69 (dd, J ϭ 8.0, J ϭ 4.4 Hz, 2 H, H1), 6.81 (dd, J ϭ
1
the solid. H NMR (400 MHz, CDCl3, 300 K, ppm): δ ϭ 1.20 (br.
8.0, J ϭ 4.4 Hz, 4 H, H2, H3), 7.28 (m, 20 H, PPh2). 13C NMR
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s, 12 H, m,p-CH2, c-C6), 1.64 (br. s, 8 H, o-CH2, c-C6), 3.61 (s, 12
H, OCH3), 6.65 (d, 1J ϭ 8.8 Hz, 4 H), 6.87 (br. s, 4 H), 7.00 (d,
(100 MHz, CDCl3, 300 K, ppm): δ ϭ Ϫ2.6, 55.5, 109.7, 124.7,
128.2 (d, JP,C ϭ 6.8 Hz), 128.5, 129.5, 133.8 (d, JP,C ϭ 19.8 Hz),
136.3, 136.7 (d, JP,C ϭ 9.9 Hz), 139.5, 161.9 (d, JP,C ϭ 15.9 Hz).
31P{1H} NMR (162 MHz, CDCl3, 300 K, ppm): δ ϭ Ϫ16.1 (s).
C40H38O2P2Si: calcd. C 74.98, H 5.98; P, 9.67; found C 75.06, H
5.93; P, 9.63.
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1J ϭ 6.4 Hz, 4 H), 7.38 (t, J ϭ 7.2 Hz, 16 H, PPh2), 7.46 (q, J ϭ
7.2 Hz, 8 H, PPh2), 7.82 (br. s, 16 H, PPh2). 31P{1H} NMR
(162 MHz, CDCl3, 300 K, ppm): δ ϭ 23.7 (d, JRhϪP ϭ 128 Hz).
IR (ATR mode, solid, carbonyl region, cmϪ1): ν
˜ ϭ 1976 (RhCO).
C90H84Cl2O6P4Rh2: calcd. C 65.03, H 5.09; found C 64.88, H 4.96.
Bis(2,2Ј-methoxy-5,5Ј-cyclohexyl)diphenylphosphane Oxide (5): Li-
gand 2 (0.65 g, 0.98 mmol) was dissolved in CH2Cl2 (25 mL) and
H2O2 (30 wt% aqueous solution) (0.20 mL, 1.96 mmol) in H2O
(20 mL) was added dropwise at 0 °C after which the two-phase
system was stirred for about 10 h at room temp. The organic layer
was washed with 0.1 NaOH solution (20 mL) and water (20 mL).
After drying with MgSO4 and subsequent filtration, the solvent
was removed in vacuo to leave a white powder. Yield 85% (0.58 g,
Molecular Structures of 1؊3 and 5؊8: The data were collected on
a NoniusϪKappa CCD diffractometer with a rotating anode. The
structures were solved by direct methods using SHELXS-97 (2,
3)[47] or DIRDIF99 (1, 6Ϫ8)[48] and refined by least-squares pro-
cedures on F2 using SHELXL-97.[49] All non-hydrogen atoms were
refined with anisotropic displacement parameters. Hydrogen atoms
were constrained to idealized geometries and allowed to ride on
their carrier atoms with an isotropic displacement parameter re-
lated to the equivalent displacement parameter of their carrier
atoms. Compound 3 contained one phenyl ring on one of the phos-
phanes which is disordered over two positions. Compound 6 con-
tained four molecules of CDCl3 in the unit cell. Compound 7 con-
tained two acetone molecules which were disordered over two posi-
tions. Compound 8 contained disordered dichloromethane mol-
ecules. Their contribution was taken into account using the
PLATON/SQUEEZE procedure. Structure validation and molecu-
lar graphics preparation were performed with the PLATON pack-
age.[50] Crystal data are given in Tables 6 and 7. CCDC-213681
(1), -213682 (2), -213683 (3), -213684 (5), -213685 (6), -213686 (7),
and -213687 (8) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the CCDC, 12
Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-
1
0.83 mmol). H NMR (400 MHz, CDCl3, 300 K, ppm): δ ϭ 1.46
(s, 6 H, m,p-CH2, c-C6), 2.18 (s, 4 H, o-CH2, c-C6), 3.55 (s, 6 H,
1
2
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OCH3), 6.81 (dd, J ϭ 8.8, J ϭ 5.6 Hz, 2 H, H1), 7.32 (dd, J ϭ
8.8, 2J ϭ 2.4 Hz, 2 H, H2), 7.41 (dt, J ϭ 8.0, 2J ϭ 2.4 Hz, 8 H, o-
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CH, PPh), 7.51 (dt, J ϭ 8.4, J ϭ 1.2 Hz, 4 H, p-CH, PPh), 7.65
(d, J ϭ 2.4 Hz, 2 H, H3), 7.69 (q, J ϭ 4.8 Hz, 8 H, m-CH, PPh).
13C NMR (100 MHz, CDCl3, 300 K, ppm): δ ϭ 22.7, 26.1, 37.0,
45.3, 55.2, 111.3 (d, JP,C ϭ 7.6 Hz), 128.0 (d, JP,C ϭ 12.3 Hz), 131.3
1
1
(d, JP,C ϭ 10.8 Hz), 132.8, 133.2, 133.9, 141.0, 158.6 (d, JP,C
ϭ
3.7 Hz). 31P{1H} NMR (162 MHz, CDCl3, 300 K, ppm): δ ϭ 27.7
(s). C44H42O4P2: calcd. C 75.85, H 6.08; found C 76.04, H 6.14.
trans,trans-[PdClCH3-2]2, Complex 6: Ligand 2 (40.2 mg, 60.5
µmol) and [PdClCH3(cod)] (13.9 mg, 52.4 µmol) were dissolved in
CDCl3 (0.5 mL) and the solution was stirred for 2 h before the
solution was analyzed by NMR spectroscopy. Single crystals were 1223-336033; E-mail: deposit@ccdc.cam.ac.uk].
Eur. J. Inorg. Chem. 2003, 4361Ϫ4369
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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