Synthesis of Some Di- and Tetraphosphonic Acids by Suzuki Cross-Coupling

Article abstract of DOI:10.1002/zaac.201800197

Five diphosphonic acids, namely, benzene-1,4-bis-p-phenylphosphonic acid (1), anthracene-9,10-bis-p-phenylphosphonic acid (2), benzene-1,2-bis-p-phenylphosphonic acid (3), benzene-1,3-bis-p-phenylphosphonic acid (4), and biphenyl-4,4′-bis-p-phenylphosphonic acid (5) as well as three tetraphosphonic acids, namely, benzene-1,2,4,5-tetrakis-p-phenylphosphonic acid (6), tetrabiphenylsilane tetrakis-4-phosphonic acid (7), and pyrene-1,3,6,8-tetrakis-p-phenylphosphonic acid (8) and their dimethyl esters 1a–8a were prepared via Suzuki cross-coupling reactions involving p-dimethylphosphonatophenylboronic acid and brominated aromatics. The Suzuki cross-coupling occurs under milder conditions than the transition metal catalyzed Arbuzov reaction usually applied for the preparation of dialkyl phosphonates. For the same starting material both reactions are complementary and yield phosphonic acids with different spacer lengths, which was exemplified for tetrakis(4-bromophenyl)silane. Suzuki cross-coupling gives rise to 7, whereas the Arbuzov reaction produces tetraphenylsilane tetrakis-4-phosphonic acid.

Full text of DOI:10.1002/zaac.201800197

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201800197
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Synthesis of Some Di- and Tetraphosphonic Acids by Suzuki
Cross-Coupling
Alexandra Schütrumpf,[a] Andrew Duthie,[b] Enno Lork,[a] Gündog˘ Yücesan,[c] and Jens Beckmann*[a]
Abstract. Five diphosphonic acids, namely, benzene-1,4-bis-p-phenyl-
phosphonic acid (1), anthracene-9,10-bis-p-phenylphosphonic acid (2),
boronic acid and brominated aromatics. The Suzuki cross-coupling oc-
curs under milder conditions than the transition metal catalyzed Arbu-
benzene-1,2-bis-p-phenylphosphonic acid (3), benzene-1,3-bis-p-phen- zov reaction usually applied for the preparation of dialkyl phosphona-
ylphosphonic acid (4), and biphenyl-4,4Ј-bis-p-phenylphosphonic acid tes. For the same starting material both reactions are complementary
(5) as well as three tetraphosphonic acids, namely, benzene-1,2,4,5- and yield phosphonic acids with different spacer lengths, which was
tetrakis-p-phenylphosphonic acid (6), tetrabiphenylsilane tetrakis-4-
phosphonic acid (7), and pyrene-1,3,6,8-tetrakis-p-phenylphosphonic
exemplified for tetrakis(4-bromophenyl)silane. Suzuki cross-coupling
gives rise to 7, whereas the Arbuzov reaction produces tetraphenyl-
acid (8) and their dimethyl esters 1a–8a were prepared via Suzuki silane tetrakis-4-phosphonic acid.
cross-coupling reactions involving p-dimethylphosphonatophenyl-
Introduction
the limitless potential of the porous metal organophosphonates
Metal organophosphonates constitute a unique class of po-
rous materials, which recently received tremendous attention
in material science.[1–4] For instance, porous metal organic
frameworks (MOFs) or proton-conducting membranes (PCMs)
for fuel cells based on metal organophosphonates are thermally
more stable and hydrolytically less sensitive than their carb-
oxylate counterparts.[5,6] Up to the early 2000s, most metal-
organophosphonates possessed highly dense pillared-layered
and lamellar structures because their syntheses relied on struc-
turally flexible alkylphosphonate linkers.[7–9] More recently,
with the introduction of the rigid tetratopic arylphosphonate
linkers, such as the square planar tetra(4-phosphonophenyl)
porphyrin[10] and the tetrahedral tetraphenylmethane tetrakis-
4-phosphonic acid[11] precluded the formation of dense 2D
metal oxide layers. Their introduction has increased the dis-
tances between the organophosphonate adhesive units and fa-
vored the formation of metal oxide clusters and stable one-
dimensional inorganic building units to form one-dimensional
hexagonal void channels or porous diamandoid networks. Ar-
ylphosphonates have shown to be important in void space for-
mation as the structural rigidity of the aromatic linkers was
essential to maintain the distance between the phosphonate
binding units. All these studies suggested that the nature of the
bridging ligand is the most important factor defining the struc-
ture of metal organophosphonates and their functions. Despite
in material science, the number of aromatic bridging ligands
in phosphonate chemistry is still too limited to conduct more
comprehensive studies to create novel metal arylphosphonates
and identify their basic patterns to perform the isoreticular syn-
thesis to control the pore sizes.[2] The different geometric ori-
entations expanding tether lengths and geometrical orientations
such as V- and X-shaped ligands have not been studied yet
due to the synthetic challenges in the preparation of suitable
arylphosphonic acids. The vast majority of dialkyl arylphos-
phonates is prepared via a transition metal catalyzed variant of
the Arbuzov reaction, which is often notoriously sluggish.[12]
Typical synthetic protocols require temperatures above 150 °C
for several hours, during which the catalysts often need to be
added in small portions plus several days under reduced pres-
sure to remove the solvents completely. Despite some im-
provements in recent years,[13,14] the yields are still un-
satisfying particularly for target molecules with multiple phos-
phonate sites. The number of commercially or synthetically
available brominated aromatics suitable as starting materials is
also limited especially with respect to the increasing tether
lengths and multiple phosphonate sites. In addition, the re-
gioselective bromination of aromatic compounds is still an
emerging field of science[15] and it would be time consuming
to follow the bromination path to create brominated aryl scaf-
folds to synthesize the corresponding arylphosphonic acids. In
this work, we describe the preparation of dimethyl arylphos-
phonates via Suzuki cross-coupling reactions[16] using p-di-
methylphosphonato-phenylboronic acid, a reagent that has
been reported only in the patent literature.[17] The Suzuki
cross-coupling occurs under substantially milder conditions
(refluxing toluene) than the metal-catalyzed Arbuzov reaction.
The dimethyl arylphosphonates were subsequently converted
by hydrolysis into previously known and new di- and tetra-
phosphonic acids, which might find applications in material
science in the future.
* Prof. Dr. J. Beckmann
E-Mail: j.beckmann@uni-bremen.de
Homepage: http://www.uni-bremen.de/de/beckmann/
[a] Institut für Anorganische Chemie und Kristallographie
Universität Bremen
Leobener Straße 7, 28359 Bremen, Germany
[b] School of Life and Environmental Sciences
Deakin University
Pigdons Road, Waurn Ponds 3217, Australia
[c] Department of Food Chemistry and Toxicology
Technische Universität Berlin
Gustav-Meyer-Allee 25, 13355 Berlin, Germany
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cage molecules following up the mechanism previously re-
Results and Discussion
ported.[20–23] Likewise, the anthracene core in 2 has significant
potential to form void spaces due to the T-shape of the central
aryl core and difficulty of such linker arrangements to form
dense pillared layered networks. The number of metal com-
plexes synthesized using 1 is very limited.[24–26] The linear
diphosphonic acid 5, a structural analogue of 1 with longer
tether length, was claimed in the literature, however, no details
about its preparation, use and characterization have been dis-
closed.[26] From the tetraphosphonic acids, 6 was described
previously,[27] whereas 7 and 8 are new compounds. The tetra-
biphenylsilane tetrakis-4-phosphonic acid (7) is a topological
analog of tetraphenylmethane tetrakis-4-phosphonic acid and
tetraphenylsilane tetrakis-4-phosphonic acid,[28] which was re-
cently used for the preparation of Cu and Zn-based MOFs
showing very high surface areas.[11,29] Notably, both tetraphos-
phonic acids were prepared from the same starting material,
namely tetrakis(4-bromophenyl)silane. In this notion, the com-
mon transition metal-catalyzed Arbuzov reaction[28] and the
Suzuki cross-coupling reaction applied herein are complemen-
tary methods giving rise to different space lengths, e.g. phenyl
vs. biphenyl. The number of reported tetratopic planar aryl-
phosphonate linkers are limited to porphyrin and pyrene scaf-
folds and there are two articles, in which the porous networks
are reported using the porphyrin tetrakis-p-phenylphosphonic
acid[10] and tetraethyl-1,3,6,8-pyrenetetraphosphonate mono-
ester.[30] Both ligands formed void channels via coordination
The reaction of p-dimethylphosphonatophenylboronic acid
with di- and tetrabrominated aromatics and sodium carbonate
in the presence of catalytic amounts of tetrakis(triphenylphos-
phine)palladium in refluxing toluene afforded five diphos-
phonic dimethyl esters 1a–5a (Scheme 1) and three tetraphos-
phonic dimethyl esters 6a–8a (Scheme 2), which were isolated
after column chromatography in yields between 26 and 87%.
The dimethyl phosphonates 1a–5a were obtained as (micro-)
crystalline solids that are well soluble in common organic sol-
vents, such as chloroform, toluene or THF. The quantitative
1
characterization of 1a–5a was achieved by H, 13C, and 31P-
NMR spectroscopy, which, besides the microanalysis, con-
firmed the analytical purity of the bulk materials. The molecu-
lar structures of 1a, 2a, 4a, and 6a were established by single-
crystal X-ray crystallography, which provided independent
confirmation for the identity of these compounds (Figure 1).
The hydrolysis of 1a–5a with conc. hydrochloric acid gave
rise to the diphosphonic acids 1–5 (Scheme 1) and the tetra-
phosphonic acids 6–8, which were isolated in 72% to nearly
quantitative yields (Scheme 2). The linear diphosphonic acids,
1 and 2 were previously reported,[18,19] whereas the structural
isomers of 1, namely, 3 and 4 were unknown. The synthesis
of the V-shaped arylphosphonate linkers 3 and 4 is especially
useful with respect to the formation of molecular cage struc-
tures in conjunction with the corner forming auxiliary ligands.
The concurrent use of 1, 3, 4, and 5 for the preparation of
MOFs would be significant to form expanding macrocycle or of tetratopic tetragonal planar arrangements with one-dimen-
Scheme 1. Synthesis of diphosphonic acids 1–5 and their dimethyl esters 1a–5a.
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Scheme 2. Synthesis of tetraphosphonic acids 6–8 and their dimethyl esters 6a–8a.
sional inorganic building units. The phosphonic acid 8 was were recorded, which showed single resonances for 2, 4, and
constructed on the same pyrene core with expanding phenyl 7 at δ = 18.6, 16.2, and 18.7 ppm, respectively.
arms at the same 1,3,6,8 positions forming a platform poten-
tially leading to larger void spaces. All phosphonic acids 1–8
are virtually insoluble in chloroform, toluene, or THF, which
Conclusions
might be attributed to extensive intermolecular hydrogen bond-
ing of the phosphonate groups and π stacking of the aromatic
rings.[28] The solubility of 1, 3, 4, and 7 in methanol or DMSO
was sufficiently high for their NMR characterization. How-
ever, all phosphonic acids are soluble in 1 m sodium hydroxide
solution, which effects deprotonation. In this way, the phos-
phonates derived from 1–8 were characterized by 1H, 13C, and
31P NMR spectroscopy. From acetonitrile solutions of 1–8
ESI-MS spectra, recorded in the negative detection mode, also
In this paper we report a new strategy utilizing the Suzuki
cross-coupling reactions to synthesize arylphosphonate linkers
with expanding tether lengths that could be employed in the
synthesis of isoreticular MOFs exhibiting larger pore dia-
meters. Using this strategy, we have created a large library of
longer branched arylphosphonates and dimethyl arylphosphon-
ates starting with simple p-dimethylphosphonatophenylboronic
acid and brominated aromatics. We are currently performing
more comprehensive and systematic studies to establish the
showed indicative mass clusters related to the phosphonate structural patterns of metal-arylphosphonates to engineer the
ions. For selected phosphonic acids, 31P MAS NMR spectra void channels using the reported new linker arrangements.
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was used both as a drying gas and for nebulization with flow rates of
approximately 5 L·min–1 and a pressure of 5 psi, respectively. Pressure
in the mass analyzer region was usually about 1ϫ10–5 mbar. Spectra
were collected for 1 min and averaged. Microanalyses were carried
out by the Analytische Laboratorien GmbH (Lindlar, Germany).
Synthesis of p-Dimethylphosphonatophenylboronic Acid:[17]
A
mixture of p-bromophenylboronic acid (10.0 g, 49.8 mmol) and tri-
methyl phosphit (92.6 g, 746 mmol) in toluene (400 mL) was heated
under reflux. During 6 h, a solution of tri-n-butyltin hydride (17.4 g,
59.7 mmol) and azo-bis(isobutyronitrile) (1.22 g, 1.47 mmol) in tolu-
ene (300 mL) was added. Subsequently, the reaction mixture was
heated under reflux for 12 h. The solvent was removed under reduced
pressure and the crude product purified by column chromatography
(silica gel, ethyl acetate). The product was obtained as colorless solid
(9.41 g, 40.9 mmol, 82%; Mp. 108 °C).
1H NMR (200 MHz, CD3OD): δ = 7.95–7.81 (m, 2 H, H-3), 7.73 [dd,
3
2 H, 3J(1H-1H) = 8.1, J(1H-31P) = 13.1 Hz, H-2], 3.76 [d, 6 H, 3J(1H-
31P) = 11.1 Hz, CH3] ppm. 11B-{1H} NMR (115 MHz, CD3OD): δ =
29.7 ppm. 13C{1H} NMR (50 MHz, CD3OD): δ = 134.9 [d, 2J(13C-
3
31P) = 14.8 Hz, C-2], 131.6 [d, J(13C-31P) = 9.7 Hz, C-3], 131.2 [d,
4J(13C-31P) = 9.1 Hz, C-4], 128.5 [d, 1J(13C-31P) = 188.8 Hz, C-1],
53.5 [d, 2J(13C-31P) = 5.8 Hz, CH3] ppm. 31P{1H} NMR (81 MHz,
CD3OD): δ = 23.5 [1J(31P-13C) = 188.8 Hz] ppm. ESI MS: m/z = 253.0
[M + Na]+, calcd. for C8H12BNaO5P = 253.0 g·mol–1.
Synthesis of 1,4-Bis(p-dimethylphosphonatophenyl)benzene (1a):
A mixture of 1,4-dibromobenzene (1.00 g, 4.23 mmol), p-dimethyl-
phosphonatophenylboronic acid (3.89 g, 17.2 mmol), sodium carb-
onate (1.79 g, 17.3 mmol) and tetrakis(triphenylphosphine)palladium
(0.24 g, 0.21 mmol) in toluene (50 mL), ethanol (25 mL) and water
(25 mL) was heated under reflux for 24 h. To the reaction mixture,
water (50 mL) was added and the aqueous layer extracted with dichlo-
romethane (3ϫ50 mL). The combined organic layers were washed
with saturated brine (50 mL) and dried with sodium sulfate. Removal
of volatiles under reduced pressure and purification by column
chromatography (silica; dichloromethane / methanol = 20:1) afforded
the product as a colorless solid. Recrystallization from dichlorometh-
ane / hexane furnished colorless crystals of 1a (1.26 g, 2.82 mmol,
67%; Mp. 161 °C).
Figure 1. Molecular structures of 1a, 2a, 4a, and 6a showing 30%
probability ellipsoids and essential atomic numbering.
Experimental Section
General: 9,10-Dibromoanthracene[31] and tetrakis(4-bromophenyl)-
silane[32] were prepared according to the literature. All other reagents
were obtained commercially and used as received. Dry Solvents were
1H NMR (200 MHz, CDCl3): δ = 7.98–7.81 (m, 4 H, arom.-H), 7.80–
7.65 (m, 8 H, arom.-H), 3.80 [d, 12 H, 3J(1H-31P) = 11.1 Hz, CH3]
ppm. 13C{1H} NMR (50 MHz, CDCl3): δ = 144.5 [d, 4J(13C-31P) =
3.0 Hz, C-4], 139.6 (C-5), 132.4 [d, 3J(13C-31P) = 10.1 Hz, C-3], 127.8
1
collected from a SPS800 mBraun solvent system. The H-, 13C-, 19F-
29Si-, and 31P-NMR spectra were recorded at room temperature with
a Bruker Avance-360 spectrometer and are referenced to SiMe4 (1H,
13C, 29Si,), CCl3F (19F), and H3PO4 (31P). IR spectra were measured
with a Perkin-Elmer Paragon 500 FT-IR spectrometer. Electron impact
mass spectrometry (EI MS) was carried out with a Finnigan MAT 95.
The ESI MS spectra were obtained with a Bruker Esquire-LC ion trap
MS. Acetonitrile solutions (c = 1ϫ10–6 mol·L–1) were injected di-
rectly into the spectrometer at a flow rate of 3 μL·min–1. Nitrogen
1
(C-6), 127.1 [d, 2J(13C-31P) = 15.3 Hz, C-2], 125.7 [d, J(13C-31P) =
190.7 Hz, C-1], 52.7 [d, 2J(13C-31P) = 5.5 Hz, CH3] ppm. 31P{1H}
NMR (81 MHz, CDCl3): δ = 22.9 ppm. C22H24O6P2 (446.37): calcd.
C 59.20; H 5.42%; found: C 59.11; H 5.35%. EI MS: m/z = 446.37
[M]+, calcd. for C22H24O6P2 = 446.36 g·mol–1.
Synthesis of 9,10-Bis(p-dimethylphosphonatophenyl)anthracene
(2a): A mixture of 9,10-dibromoanthracene (1.00 g, 2.97 mmol), p-
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dimethylphosphonatophenylboronic acid (2.73 g, 11.9 mmol), sodium
carbonate (1.26 g, 11.9 mol), and tetrakis(triphenylphosphine)palla-
dium (0.17 g, 0.15 mmol) was treated as described for 1a. Purification
by column chromatography (silica; ethyl acetate / methanol = 20:1)
and recrystallization from dichloromethane / hexane afforded yellow
crystals of 2a (1.26 g, 2.23 mmol, 77%; Mp. Ͼ 230 °C).
1H NMR (200 MHz, CDCl3): δ = 7.98–7.51 (m, 12 H, arom.-H), 3.79
3
[d, 12 H, J(1H-31P) = 11.1 Hz, CH3] ppm. 13C{1H} NMR (50 MHz,
4
CDCl3): δ = 145.0 [d, J(13C-31P) = 3.0 Hz, C-4], 140.7 (C-5), 132.4
[d, 3J(13C-31P) = 10.2 Hz, C-3], 129.6, 127.3 [d, 2J(13C-31P) = 15.4 Hz,
C-2], 127.1, 126.3, 125.8 [d, 1J(13C-31P) = 190.2 Hz, C-1], 52.7 [d,
2J(13C-31P) = 5.5 Hz, CH3] ppm. 31P{1H} NMR (81 MHz, CDCl3): δ
= 22.8 [1J(31P-13C) = 190.7 Hz] ppm. C22H24O6P2 (446.37): calcd. C
59.20; H 5.42%; found: C 59.05; H 5.32%. ESI MS: m/z = 469.36
[M + Na]+, Calcd. for C22H24NaO6P2 = 469.36 g·mol–1.
3
1H NMR (200 MHz, CDCl3): δ = 8.0 [dd, 4 H, J(1H-1H) = 8.2 Hz,
arom.-H], 7.67–7.53 (m, 8 H, arom.-H), 7.43–7.29 (m, 4 H, arom.-H),
3.92 [d, 12 H, 3J(1H-31P) = 11.1 Hz, CH3] ppm. 13C{1H} NMR
(50 MHz, CDCl3): δ = 143.7 [d, J(13C-31P) = 3.0 Hz, C-4], 136.1 (C-
4
Synthesis of 4,4Ј-Bis(p-dimethylphosphonatophenyl)biphenyl (5a):
A mixture of 4,4Ј-dibromobiphenyl (0.50 g, 1.60 mmol), p-dimethyl-
phosphonatophenylboronic acid (1.47 g, 6.41 mmol), sodium carb-
onate (0.68 g, 6.41 mmol) and tetrakis(triphenylphosphine)palladium
(0.09 g, 0.08 mmol) was treated as described for 1a. Purification by
column chromatography (silica, dichloromethane / methanol = 20:1)
afforded a colorless solid of 5a [0.58 g, 1.11 mmol, 69%; Mp. 210 °C
(decomposition)].
5), 131.9 [d, 3J(13C-31P) = 10.2 Hz, C-3], 131.5 [d, 2J(13C-31P) =
15.2 Hz, C-2], 129.4, 126.4 [d, 1J(13C-31P) = 190.8 Hz, C-1], 126.5,
125.5, 52.9 [d, 2J(13C-31P) = 5.6 Hz, CH3] ppm. 31P{1H} NMR
(81 MHz, CDCl3): δ = 22.8 ppm. UV (CH2Cl2): λmax = 261, 355, 375,
395 nm. C30H28O6P2 (546.49): calcd. C 65.93; H 5.16%; found: C
66.07; H 5.24%. EI MS: m/z = 546.49 [M]+, calcd. for C30H28O6P2 =
546.49 g·mol–1.
Synthesis of 1,2-Bis(p-dimethylphosphonatophenyl)benzene (3a).
A mixture of 1,2-dibromobenzene (0.50 g, 2.12 mmol), p-dimethyl-
phosphonatophenylboronic acid (0.89 g, 8.47 mmol), sodium carb-
onate (0.89 g, 8.47 mol), and tetrakis(triphenylphosphine)palladium
(0.12 g, 0.10 mmol) was treated as described for 1a. Purification by
column chromatography (silica; dichloromethane / methanol = 20:1)
afforded a colorless solid of 3a (0.38 g, 0.85 mmol, 40%; Mp. 91 °C).
1H NMR (200 MHz, CDCl3): δ = 7.98–7.82 (4H, m, arom.-H), 7.88–
7.69 (12H, m, arom.-H), 3.81 [d, 12 H, 3J(1H-31P) = 11.1 Hz, CH3]
ppm. 13C{1H} NMR (50 MHz, CDCl3): δ = 144.8 [d, 4J(13C-31P) =
3.4 Hz, C-4], 140.2 (C-8), 139.0 [d, 5J(13C-31P) = 1.13 Hz, C-5], 132.5
[d, J(13C-31P) = 10.2 Hz, C-3], 127.7, 127.5, 127.1 [d, J(13C-31P) =
15.3 Hz, C-2], 125.5 [d, 1J(13C-31P) = 190.7 Hz, C-1], 52.7 [d, 2J(13C-
31P) = 5.5 Hz, CH3] ppm. 31P{1H} NMR (81 MHz, CDCl3): δ = 23.0
[1J(31P-13C) = 190.5 Hz] ppm. C28H28O6P2 (522.46): calcd. C 64.37;
H 5.40%; found: C 64.43; H 5.44%. EI MS: m/z = 522.46 [M]+, calcd.
for C28H28O6P2 = 522.46 g·mol–1.
3
2
Synthesis of 1,2,4,5-Tetrakis(p-dimethylphosphonatophenyl)benz-
1H NMR (200 MHz, CDCl3): δ = 7.72–7.55 (m, 4 H, arom.-H), 7.51–
7.37 (m, 4 H, arom.-H), 7.27–7.16 (m, 4 H, arom.-H), 3.75 [d, 12 H,
3J(1H-31P) = 11.1 Hz, CH3] ppm. 13C{1H} NMR (50 MHz, CDCl3):
δ = 145.5 [d, 4J(13C-31P) = 3.1 Hz, C-4], 139.3 (C-5), 131.5 [d, 3J(13C-
31P) = 10.2 Hz, C-3], 130.6, 129.6 [d, 2J(13C-31P) = 15.4 Hz, C-
2],126.9, 125.0 [d, J(13C-31P) = 190.7 Hz, C-1], 52.7 [d, J(13C-31P)
= 5.5 Hz, CH3] ppm. 31P{1H} NMR (81 MHz, CDCl3): δ = 22.8
[1J(31P-13C) = 190.7 Hz] ppm. C22H24O6P2 (446.37): calcd. C 59.20;
H 5.42%; found: C 59.21; H 5.27%. EI MS: m/z = 446.37 [M]+, calcd.
for C22H24O6P2 = 446.37 g·mol–1.
ene (6a):
A
mixture of 1,2,4,5-tetrabromobenzene (0.90 g,
2.28 mmol), p-dimethylphosphonatophenylboronic acid (3.15 g,
13.7 mmol), sodium carbonate (0.96 g, 9.14 mol) and tetrakis(triphen-
ylphosphine)palladium (0.13 g, 0.11 mmol) was treated as described
for 1a. Purification by column chromatography (silica; dichlorometh-
ane / methanol = 20:1) and recrystallization from dichloromethane /
hexane afforded colorless crystals of 6a (0.50 g, 0.61 mmol, 27%; Mp.
Ͼ 230 °C).
1
2
Synthesis of 1,3-Bis(p-dimethylphosphonatophenyl)benzene (4a):
A mixture of 1,3-dibromobenzene (1.00 g, 4.23 mmol), p-dimethyl-
phosphonatophenylboronic acid (3.89 g, 17.2 mmol), sodium carb-
onate (1.79 g, 17.3 mol), and tetrakis(triphenylphosphine)palladium
(0.24 g, 0.21 mmol) was treated as described for 1a. Purification by
column chromatography (silica; dichloromethane / methanol = 20:1)
and recrystallization from dichloromethane / hexane afforded colorless
crystals of 4a (1.65 g, 3.69 mmol, 87%; Mp. 107 °C).
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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,
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Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Synthesis of Benzene-1,2-bis-p-phenylphosphonic Acid (3): A sus-
ppm. 13C{1H} NMR (50 MHz, 1 m NaOH in D2O): δ = 140.3 [d,
pension of 3a (0.38 g, 0.85 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 3 (0.32 g, 0.82 mmol, 96%; Mp. Ͼ 305 °C).
4J(13C-31P) = 2.9 Hz, C-4], 140.2 [d, 1J(13C-31P) = 168.2 Hz, C-1],
3
139.5, 139.0, 131,2 [d, J(13C-31P) = 9.0 Hz, C-3], 127.5,127.4, 126.3
[d, 2J(13C-31P) = 12.9 Hz, C-2] ppm. 31P{1H} NMR (81 MHz, 1 m
NaOH in D2O): δ = 12.4 [1J(31P-13C) = 168.0 Hz] ppm. IR (KBr):ν˜ =
2923 (OH), 1145 (PO) cm–1. C24H20O6P2 (466.36): calcd. C 61.81; H
4.32%; found:
C
61.66;
H 4.22%. ESI MS: m/z = 509.31
–
[M-3H+2Na] , calcd. for C24H17Na2O6P2 = 509.31 g·mol–1.
Synthesis of Benzene-1,2,4,5-tetrakis-p-phenylphosphonic Acid (6):
A suspension of 6a (0.40 g, 0.49 mmol) in a 24% solution of HCl in
water (50 mL) was heated under reflux for 2 d. The solvent was re-
moved to give a colorless solid of 6 (0.25 g, 0.36 mmol, 73%;
Mp. Ͼ 230 °C).
1H NMR (200 MHz, CDOD3): δ = 7.62–7.47 (m, 4 H, arom.-H), 7.43–
7.30 (m, 4 H, arom.-H), 7.20–7.09 (m, 4 H, arom.-H), ppm. 13C{1H}
NMR (50 MHz, CDOD3): δ = 145.2 [d, 4J(13C-31P) = 2.9 Hz, C-4],
140.0 (C-5), 130.7, 130.7 [d, 3J(13C-31P) = 10.3 Hz, C-3], 130.3 [d,
1J(13C-31P) = 186.7 Hz, C-1]129.9 [d, 2J(13C-31P) = 15.1 Hz, C-
2],128.3 ppm. 31P{1H} NMR (81 MHz, CDOD3): δ = 17.3 [1J(31P-
13C) = 186.0 Hz] ppm. IR (KBr):ν˜ = 2923 (OH), 1183 (PO) cm–1.
C18H16O6P2 (390.26): calcd. C 55.40; H 4.13%; found: C 55.51; H
4.01%. ESI MS: m/z = 389.26 [M – H]–, calcd. for C18H15O6P2
389.26 g·mol–1.
=
1H NMR (200 MHz, 1 m NaOH in D2O): δ = 7.63–7.36 (m, 10 H,
arom.-H), 7.29–7.12 (m, 8 H, arom.-H) ppm. 13C{1H} NMR (50 MHz,
4
1 m NaOH in D2O): δ = 141.1 [d, J(13C-31P) = 2.8 Hz, C-4], 139.7,
Synthesis of Benzene-1,3-bis-p-phenylphosphonic Acid (4): A sus-
pension of 4a (1.60 g, 3.69 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 4 (1.21 g, 3.10 mmol, 84%; Mp. Ͼ 230 °C).
1
3
139.5 [d, J(13C-31P) = 167.4 Hz, C-1], 133.4, 130.3 [d, J(13C-31P) =
8.9 Hz, C-3], 129.3 [d, 2J(13C-31P) = 12.8 Hz, C-2] ppm. 31P{1H}
NMR (81 MHz, 1 m NaOH in D2O): δ = 12.4 [1J(31P-13C) = 167.8 Hz]
ppm. IR (KBr):ν˜ = 2924 (OH), 1144 (PO) cm–1. C30H26O12P4
(702.41): calcd. C 51.30; H 3.73%; found: C 51.32; H 3.69%. ESI
MS: m/z = 371.8 [M-4H+2Na]2–, calcd. for C30H22Na2O12P4
744.36 gmol–1 (for z = 2: 372.18 g·mol–1).
=
Synthesis of Tetrabiphenylsilane Tetrakis-4-phosphonic Acid (7):
A suspension of 7a (1.08 g, 1.00 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 colorless solid of 7 (0.88 g, 0.91 mmol, 91%;
Mp. Ͼ 230 °C).
1H NMR (200 MHz, [D6]DMSO): δ = 7.99–7.55 (m, 12 H, arom.-H),
4.91 (s, 4 H, OH) ppm. 13C{1H} NMR (50 MHz, [D6]DMSO): δ =
142.3 [d, J(13C-31P) = 3.0 Hz, C-4], 140.26, 134.9, 131.2 [d, J(13C-
31P) = 10.4 Hz, C-3], 129.8, 126.7 [d, 2J(13C-31P) = 14.3 Hz, C-2],
126.6, 125.5 ppm. 31P{1H} NMR (81 MHz, [D6]DMSO): δ = 13.9
[1J(31P-13C) = 182.7 Hz] ppm. IR (KBr):ν˜ = 2851 (OH), 1142 (PO)
cm–1. C18H16O6P2 (390.26): calcd. C 55.40; H 4.13%; found: C 55.26;
H 4.13%. ESI MS: m/z = 389.26 [M – H]–, calcd. for C18H15O6P2 =
389.26 g·mol–1
4
3
1H NMR (200 MHz, CDOD3): δ = 8.41–8.14 (32H, m, arom.-H) ppm.
13C{1H} NMR (50 MHz, CDOD3): δ = 144.3 [d, 4J(13C-31P) = 2.9 Hz,
C-4], 142.5, 138.1, 134.6, 133.4 [d, 1J(13C-31P) = 1984.9 Hz, C-1],
3
2
132.7 [d, J(13C-31P) = 10.3 Hz, C-3], 128.1, 128.0 [d, J(13C-31P) =
Synthesis of Biphenyl-4,4Ј-bis-p-phenylphosphonic Acid (5): A sus-
pension of 5a (0.40 g, 0.86 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 5 (0.29 g, 0.62 mmol, 72%; Mp. Ͼ 230 °C).
14.6 Hz, C-2] ppm. 29Si-{1H} NMR (71 MHz, CDOD3):
δ =
–14.9 ppm. 31P{1H} NMR (81 MHz, CDOD3): δ = 15.3 [1J(31P-13C)
= 184.9 Hz] ppm. IR (KBr):ν˜ = 2867 (OH), 1142 (PO) cm–1.
C48H40O12P4Si (960.80): calcd. C 60.00; H 4.20%; found: C 59.97; H
4.26%. ESI MS: m/z = 959.80 [M – H]–, calcd. for C48H39O12P4Si =
959.80 g·mol–1.
Synthesis of Pyrene-1,3,6,8-tetrakis-p-phenylphosphonic Acid (8):
A suspension of 8a (0.42 g, 0.45 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 colorless solid of 8 (0.30 g, 0.36 mmol, 81%;
1H NMR (200 MHz, 1 m NaOH in D2O): δ = 7.84–7.65 (m, 4 H,
arom.-H), 7.62–7.35 (m, 8 H, arom.-H), 7.33–7.19 (m, 4 H, arom.-H) Mp. Ͼ 230 °C).
Z. Anorg. Allg. Chem. 0000, 0–0
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ARTICLE
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age.[33] All non-hydrogen atoms were refined using anisotropic dis-
placement parameters. Hydrogen atoms attached to carbon atoms were
included in geometrically calculated positions using a riding model.
Crystal and refinement data are collected in Table 1. Figures were cre-
ated using DIAMOND.[34]
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-1842627 (1a·H2O), CCDC-1842628 (2a), CCDC-
1842629 (4a), and CCDC-1842630 (6a) (Fax: +44-1223-336-033;
E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk)
1H NMR (200 MHz, 1 m NaOH in D2O): δ = 8.02 (s, 4 H, arom.-H),
Acknowledgements
7.91(s, 2 H, arom.-H), 7.83–7.68 (m, 8 H, arom.-H), 7.55–7.43 (m, 8
H, arom.-H) ppm. 13C{1H} NMR (50 MHz, 1 m NaOH in D2O): δ =
141.6 [d, 4J(13C-31P) = 2.7 Hz, C-4], 141.0 [d, 1J(13C-31P) = 167.5 Hz,
The Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowl-
edged for financial support.
2
C-1],138.0, 131.4 [d, 3J(13C-31P) = 8.9 Hz, C-3], 130.8 [d, J(13C-31P)
= 12.8 Hz, C-2], 130.6, 128.5.0, 126.2 ppm. 31P{1H} NMR (81 MHz,
1 m NaOH in D2O): δ = 12.5 [1J(31P-13C) = 169.2 Hz] ppm. IR
(KBr):ν˜ = 2923 (OH), 1141 (PO) cm–1. UV (NaOH): λmax = 260,
300, 388 nm. UV (DMSO): λmax = 261, 303, 395 nm. C40H30O12P4
(826.55): calcd. C 58.12; H 3.66%; found: C 58.01; H 3.55%.
Keywords: Suzuki cross-coupling; Phosphonic acids;
Metall-organic frameworks (MOFs); Linker
ESI MS: m/z = 825.55 [M – H]–, calcd. for C40H29O12P4
825.55 g·mol–1.
=
References
[1] G. K. Shimizu, R. Vaidhyanathan, J. M. Taylor, Chem. Soc. Rev.
2009, 38, 1430–1449.
[2] K. J. Gagnon, H. P. Perry, A. Clearfield, Chem. Rev. 2011, 112,
Single Crystal X-ray Crystallography: Intensity data were collected
with a STOE IPDS 2T area detector (1a·H2O, 4a, 6a) and a Siemens
P4 diffractometer (2a) fitted at 173 K with graphite-monochromated
Mo-Kα (0.7107 Å) radiation. All structures were solved by direct meth-
ods and refined based on F2 by use of the SHELX program pack-
1034–1054.
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4300–4309.
Table 1. Crystal data and structure refinement of 1a, 2a, 4a, and 6a.
1a·H2O
2a
4a
6a
Formula
C22H26O7P2
464.37
C30H28O6P2
546.46
C22H24O6P2
446.35
C38H42O12P4
814.60
Formula weight /g·mol–1
Crystal system
Crystal size /mm
Space group
a /Å
b /Å
c /Å
triclinic
triclinic
monoclinic
0.5ϫ0.2ϫ0.05
C2/c
36.269(7)
6.317(1)
22.368(5)
90
121.27(3)
90
4381(2)
8
triclinic
0.5ϫ0.3ϫ0.05
0.31ϫ0.25ϫ0.18
0.5ϫ0.1ϫ0.05
¯
¯
¯
P1
P1
P1
12.340(3)
12.693(3)
15.522(3)
89.91(3)
71.37(3)
77.44(3)
2242.5(8)
4
6.544(3)
7.534(5)
13.219(6)
92.01(4)
95.75(2)
96.75(4)
643.2(6)
1
11.939(2)
12.779(3)
13.002(3)
89.38(3)
85.89(3)
83.14(3)
1964.4(7)
2
α /°
β /°
γ /°
V /Å3
Z
ρcalcd /Mg·m–3
μ (Mo-Kα) /mm–1
F(000)
1.375
0.235
976
1.411
0.214
286
1.354
0.234
1872
1.377
0.254
852
θ range /°
Index ranges
1.87 to 25.89
–15 Յ h Յ 15
–15 Յ k Յ 15
–18 Յ l Յ 18
17203
6.32 to 32.71
–8 Յ h Յ 2
–9 Յ k Յ 9
–17 Յ l Յ 17
3796
2.13 to 26.04
–44 Յ h Յ 44
–7 Յ k Յ 7
–27 Յ l Յ 24
14310
2.49 to 26.11
–14 Յ h Յ 14
–15 Յ k Յ 15
–15 Յ l Յ 15
13784
No. of reflns collected
Completeness to θ
91.8%
99.9%
98.4%
91.3%
max
No. indep. reflections
No. obsd reflections with
[I Ͼ 2σ(I)]
8004
2964
4260
7140
4243
2100
1884
3574
No. refined parameters
588
0.993
290
1.022
317
0.847
525
0.913
GooF (F2)
R1 (F) [I Ͼ 2σ(I))
wR2 (F2) (all data)
Largest diff peak/hole /e·Å–3
0.0696
0.2077
0.583 / –0.367
0.0691
0.1941
0.780 / –0.472
0.0583
0.1497
0.417 / –0.237
0.0628
0.1876
0.781/ –0.558
Z. Anorg. Allg. Chem. 0000, 0–0
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Journal of Inorganic and General Chemistry
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Received: May 11, 2018
Published online: ᭿
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
A. Schütrumpf, A. Duthie, E. Lork, G. Yücesan,
J. Beckmann* .................................................................. 1–10
Synthesis of Some Di- and Tetraphosphonic Acids by Suzuki
Cross-Coupling
Z. Anorg. Allg. Chem. 0000, 0–0
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