Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
3
1H NMR (200 MHz, CDCl3): δ = 7.68 [dd, 8 H, J(1H-1H) = 8.2 Hz, 3J(1H-31P) = 11.1 Hz, CH3] ppm. 13C{1H} NMR (50 MHz, CDCl3): δ
4
3
= 145.0 [d, J(13C-31P) = 3.1 Hz, C-4], 136.4 (C-5), 132.0 [d, J(13C-
arom.-H], 7.50 (s, 2 H, H-6), 7.35–7.23 (m, 8 H, arom.-H), 3.76 [d,
24 H, 3J(1H-31P) = 11.1 Hz, CH3] ppm. 13C{1H} NMR (50 MHz,
31P) = 10.1 Hz, C-3], 130.7 [d, 2J(13C-31P) = 15.3 Hz, C-2], 129.2,
128.3, 126.1 [d, J(13C-31P) = 190.3 Hz, C-1], 125.7, 125.5, 52.8 [d,
2J(13C-31P) = 5.6 Hz, CH3] ppm. 31P{1H} NMR (81 MHz, CDCl3): δ
= 22.7 [1J(31P-13C) = 190.3 Hz] ppm. UV (DCM): λmax = 230, 250,
301, 388 nm. C48H46O12P4 (938.77): calcd. C 61.41; H 4.94%; found:
C 61.39; H 4.79%. EI MS: m/z = 938.77 [M]+, calcd. for C48H46O12P4
= 938.77 g·mol–1.
4
CDCl3): δ = 144.3 [d, J(13C-31P) = 3.0 Hz, C-4], 139.3, 132.9, 131.7
1
2
[d, 3J(13C-31P) = 10.2 Hz, C-3], 129.8 [d, J(13C-31P) = 15.3 Hz, C-2],
1
2
125.7 [d, J(13C-31P) = 190.8 Hz, C-1], 52.7 [d, J(13C-31P) = 5.6 Hz,
CH3] ppm. 31P{1H} NMR (81 MHz, CDCl3): δ = 22.5 [1J(31P-13C) =
190.7 Hz] ppm. C38H42O12P4 (814.63): calcd. C 56.03; H 5.20%;
found: C 55.92; H 5.22%. EI MS: m/z = 814.63 [M]+, calcd. for
C38H42O12P4 = 814.63 g·mol–1.
Synthesis of Dimethyltetrabiphenylsilane Tetrakis-4-phosphonate
(7a): A mixture of tetrakis(4-bromophenyl)silane (1.00 g, 1.54 mmol),
p-dimethylphosphonatophenylboronic acid (0.65 g, 9.26 mmol), so-
dium carbonate (0.65 g, 6.17 mmol), and tetrakis(triphenylphosphine)
palladium (0.09 g, 0.07 mmol) was treated as described for 1a. Purifi-
cation by column chromatography (silica; ethyl acetate / methanol =
10:1) afforded a colorless solid of 7a (1.42 g, 1.32 mmol, 86%;
Mp. Ͼ 230 °C).
Synthesis of Benzene-1,4-bis-p-phenylphosphonic Acid (1): A sus-
pension of 1a (0.95 g, 2.13 mmol) in a 24% solution of HCl in water
(50 mL) was heated under reflux for 2 d. The solvent was removed to
give a colorless solid of 1 (0.73 g, 1.87 mmol, 92%; Mp. 161 °C).
1H NMR (200 MHz, [D6]DMSO): δ = 1.38–7.15 (m, 12 H, arom.-H),
1.96 (s, 4 H, OH) ppm. 13C{1H} NMR (50 MHz, [D6]DMSO): δ =
141.9 [d, 4J(13C-31P) = 3.0 Hz, C-4] 139.0 [d, 5J(13C-31P) = 0.9 Hz,
1H NMR (200 MHz, CDCl3): δ = 7.97–7.81 (m, 8 H, arom.-H), 7.80–
C-5], 133.1 [d, J(13C-31P) = 182.7 Hz, C-1], 131.3 [d, J(13C-31P) =
10.2 Hz, C-3], 127.6 (C-6), 126.4 [d, 2J(13C-31P) = 14.3 Hz, C-2] ppm.
31P{1H} NMR (81 MHz, [D6]DMSO): δ = 13.9 [1J(31P-13C) =
1
3
3
7.60 (m, 24 H, arom.-H), 3.79 [d, 24 H, J(1H-31P) = 11.1 Hz, CH3]
ppm. 13C{1H} NMR (50 MHz, CDCl3): δ = 144.9 [d, 4J(13C-31P) =
3.0 Hz, C-4], 141.2 (C-5), 136.9, 133.5, 132.4 [d, 3J(13C-31P) =
182.7 Hz] ppm. IR (KBr):ν˜
C18H16O6P2 (390.26): calcd. C 55.40; H 4.13%; found: C 55.43; H
4.23%. ESI MS: m/z
457.22 [M-2H+3Na]+, calcd. for
C18H14Na3O6P2 = 457.22 g·mol–1.
=
2884 (OH), 1144 (PO) cm–1.
2
10.2 Hz, C-3], 127.2 [d, J(13C-31P) = 15.4 Hz, C-2], 126.9, 125.8 [d,
1J(13C-31P) = 190.7 Hz, C-1], 52.7 [d, 2J(13C-31P) = 5.5 Hz, CH3] ppm.
29Si-{1H} NMR (71 MHz, CDCl3): δ = –14.3 ppm. 31P{1H} NMR
=
(81 MHz, CDCl3):
C56H56O12P4Si (1073.02): calcd.
C 62.58; H 5.18%. ESI MS: m/z = 1096.00 [M + Na]+, calcd. for
C56H56O12P4SiNa = 1096.00 g·mol–1.
δ
=
22.8 [1J(31P-13C)
62.68;
=
190.6 Hz] ppm.
C
H 5.26%; found:
Synthesis of Anthracene-9,10-bis-p-phenylphosphonic Acid (2): A
suspension of 2a (1.26 g, 2.30 mmol) in a 24% solution of HCl in
water (50 mL) was heated under reflux for 2d. The solvent was re-
moved to give a yellow solid of 2 (1.01 g, 2.06 mmol, 90%;
Mp. Ͼ 230 °C).
Synthesis of 1,3,6,8-Tetrakis(p-dimethylphosphonatophenyl)py-
rene (8a): A mixture of 2,3,6,7-tetrabromopyrene (1.00 g, 1.93 mmol),
p-dimethylphosphonatophenylboronic acid (2.66 g, 11.5 mmol), so-
dium carbonate (0.81 g, 7.72 mol) and tetrakis(triphenylphosphine)pal-
ladium (0.11 g, 0.09 mmol) was treated as described for 1a. Purifica-
tion by column chromatography (silica, dichloromethane / methanol =
20:1) and recrystallization from dichloromethane / hexane afforded
yellow crystals of 8a (0.47 g, 0.50 mmol, 26%; Mp. Ͼ 230 °C).
1H NMR (200 MHz, 1 m NaOH in D2O): δ = 7.79–7.60 (m, 4 H,
arom.-H), 7.43–7.32 (m, 4 H, arom.-H), 7.19–7.05 (m, 4 H, arom.-H),
7.00–6.97 ,(m, 4 H, arom.-H) ppm. 13C{1H} NMR (50 MHz, 1 m
1
NaOH in D2O): δ = 141.4 [d, J(13C-31P) = 168.0 Hz, C-1], 139.7 [d,
2J(13C-31P) = 17. 4 Hz, C-2], 137.9, 131.5, 131.4 [d, 3J(13C-31P) =
10.0 Hz, C-3], 130.0, 127.6, 126.6 ppm. 31P{1H} NMR (81 MHz, 1 m
NaOH in D2O): δ = 12.6 [1J(31P-13C) = 167.9 Hz] ppm. IR (KBr):ν˜ =
2812 (OH), 1171 (PO) cm–1. UV (DMSO): λmax = 262, 358, 376,
398 nm. UV (NaOH): λmax = 258, 356, 374, 395 nm. C26H20O6P2
(490.38): calcd. C 63.68; H 4.11%; found: C 63.50; H 4.08%. ESI
MS: m/z = 489.37 [M – H]–, calcd. for C26H19O6P2 = 489.37 g·mol–1.
1H NMR (200 MHz, CDCl3): δ = 8.15 (s, 4 H, arom.-H), 8.06–7.91
(m, 12 H, arom.-H), 7.84–7.72 (m, 6 H, arom.-H), 3.85 [d, 24 H,
Z. Anorg. Allg. Chem. 0000, 0–0
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