Tetra-hydroxy-calix[4]arene derivatives with two P(III) or P(V) units attached at the upper rim

Article abstract of DOI:10.1016/j.poly.2012.11.040

5,17-Bis(diphenylphosphino)-25,26,27,28-tetra-hydroxy-calix[4]arene (2) and the corresponding bis-(phosphine oxide) (3) and bis-(phosphine sulfide) (4) have been synthesized. A single crystal X-ray diffraction study was carried out for bis(phosphine oxide) 3, which revealed a pinched cone conformation for the calixarene core. In the solid state, each calixarene is linked to two other calixarenes via hydrogen bonds involving the phosphoryl groups as well as two of the four hydroxyl groups, thereby generating a supramolecular polymeric structure. Selective formation of chelate complexes from diphosphine 2 failed, probably because of rapid trans annular rotation of the phenoxyl groups that prevents appropriate ligand preorganisation. Upon reaction with appropriate Ru-, Rh-, and Ir-complexes, ligand 2 readily formed dinuclear complexes. One of them, namely the complex [2·{RhCl(1,5-cyclooctadiene)}₂] was assessed in the catalytic hydrogenation of linear and cyclic olefins.

Full text of DOI:10.1016/j.poly.2012.11.040

Polyhedron 51 (2013) 70–74
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Tetra-hydroxy-calix[4]arene derivatives with two P(III) or P(V) units attached at
the upper rim
a,
b
Laure Monnereau a, David Sémeril a, , Dominique Matt , Loïc Toupet
⇑
⇑
a Laboratoire de Chimie Inorganique Moléculaire et Catalyse, UMR 7177 CNRS, Université de Strasbourg, 1 Rue Blaise Pascal, 67008 Strasbourg Cedex, France
b Institut de Physique, UMR 6251 CNRS, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
a r t i c l e i n f o
a b s t r a c t
Article history:
5,17-Bis(diphenylphosphino)-25,26,27,28-tetra-hydroxy-calix[4]arene (2) and the corresponding bis-
(phosphine oxide) (3) and bis-(phosphine sulfide) (4) have been synthesized. A single crystal X-ray dif-
fraction study was carried out for bis(phosphine oxide) 3, which revealed a pinched cone conformation
for the calixarene core. In the solid state, each calixarene is linked to two other calixarenes via hydrogen
bonds involving the phosphoryl groups as well as two of the four hydroxyl groups, thereby generating a
supramolecular polymeric structure. Selective formation of chelate complexes from diphosphine 2 failed,
probably because of rapid trans annular rotation of the phenoxyl groups that prevents appropriate ligand
preorganisation. Upon reaction with appropriate Ru-, Rh-, and Ir-complexes, ligand 2 readily formed
dinuclear complexes. One of them, namely the complex [2ꢀ{RhCl(1,5-cyclooctadiene)}2] was assessed
in the catalytic hydrogenation of linear and cyclic olefins.
Received 12 November 2012
Accepted 29 November 2012
Available online 14 December 2012
Keywords:
Calix[4]arene
Phosphine
Phosphine oxide
Phosphine sulfide
Binuclear complexes
Hydrogenation
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
nylphosphinoyl)-25,26,27,28-tetrahydroxycalix[4]arene (3) is also
reported. To date, only four other tetra-hydroxy-calixarenes
The calix[4]arene backbone constitutes one of the most
employed platforms for the preparation of highly preorganized
multidentate ligands [1–4], many of which have been used in
homogeneous catalysis [5]. We have recently described the coordi-
native properties of a series of calixarenes having two phosphino
groups grafted at the distal carbon atoms 5 and 17 (upper rim)
[6,7]. These so-called CALDIP ligands form straightforwardly tran-
sition metal chelate complexes in which the PMP angle undergoes
a periodic variation in magnitude due to a rapid fan-like motion of
the PMP plane [7–9]. The particular binding features of these li-
gands have been exploited in a variety of carbon carbon bond
forming reactions [9–14]. To date, only CALDIPs in which the phe-
nolic oxygen atoms are substituted by alkyl groups have been re-
ported. We wondered whether CALDIPs devoid of substituents
attached to the lower rim would display coordinative properties
similar to those already reported, and in particular whether chelat-
ing behaviour is still possible. In the present work we describe the
bearing phosphorus-containing substituents have been reported
[15–19].
2. Experimental
2.1. General data
All syntheses were performed in Schlenk-type flasks under dry
nitrogen. Solvents were dried by conventional methods and were
distilled immediately prior to use. Routine 1H, 13C{1H} and
31P{1H} NMR spectra were recorded by using a Bruker AVANCE
300 spectrometer. 1H NMR spectra were referenced to residual
protonated solvents (7.26 ppm for CDCl3 or 5.32 ppm for CD2Cl2),
13C chemical shifts are reported relative to deuterated solvents
(77.16 ppm for CDCl3 or 53.8 ppm for CD2Cl2) and the 31P NMR
data are given relative to external H3PO4. Elemental analyses were
performed by the Service de Microanalyse, Institut de Chimie UMR
7177 CNRS-Université de Strasbourg. 5,17-Bis(diphenylphos-
phino)-25,26,27,28-tetrabenzyloxycalix[4]arene (1) [8] was pre-
pared according to a method reported in the literature. In the
NMR data given hereafter, the bridging methylene groups of the
calix[4]arene backbone are designated by the abbreviation
ArCH2Ar.
synthesis
of
5,17-bis(diphenylphosphino)-25,26,27,28-tetra-
hydroxycalix[4]arene (2) together with two P(V) derivatives. The
coordinative properties of 2 have been investigated towards cat-
ionic and neutral complexes. The X-ray structure of 5,17-bis(diphe-
⇑
Corresponding authors. Tel.: +33 3 68 85 15 50 (D. Sémeril).
E-mail addresses: dsemeril@unistra.fr (D. Sémeril), dmatt@unistra.fr (D. Matt).
0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.11.040

L. Monnereau et al. / Polyhedron 51 (2013) 70–74
71
2.2. Synthesis of bis-phosphine, bis-phosphine oxide/sulfide and
complexes
was stirred at room temperature for 2 h. A mixture of CH2Cl2
(10 mL) and water (20 mL) was then added. After extraction of
the aqueous layer with CH2Cl2 (2 ꢁ 10 mL), the organic phases
were combined. The resulting solution was washed with water
(2 ꢁ 10 mL), then dried over Na2SO4 and evaporated under reduced
pressure to afford the bis-phosphine oxide 3 as a white solid. Yield
100% (0.511 g). 1H NMR (300 MHz, CDCl3) d: 7.58–7.34 (20H, arom.
2.2.1. General procedure for debenzylation of tetrabenzyloxycalix[4]
arene derivatives
A Schlenk tube was filled with substrate (1 equiv.), AlCl3
(4 equiv.) and toluene (50 mL). After stirring this suspension for
16 h, a saturated solution of NaCl (20 mL) was slowly added. The
aqueous layer was extracted with CH2Cl2 (2 ꢁ 20 mL), then the
combined organic layers were dried over Na2SO4. Evaporation un-
der vacuum afforded a pale yellow solid, which was recrystallised
from diethylether–petroleum ether. The product was collected by
filtration and dried under vacuum.
3
CH), 7.24–6.96 (24H, arom. CH), 6.16 (t, 2H, arom. CH of calix, JH–
3
H = 7.5 Hz), 5.90 (d, 4H, arom. CH of calix, JH–H = 7.5 Hz), 5.12 (s,
4H, CH2Ph), 4.56 (s, 4H, CH2Ph), 4.12 and 2.82 (AB spin system,
2
8H, ArCH2Ar, JH–H = 13.8 Hz). 13C{1H} NMR (75 MHz, CDCl3) d:
4
158.97 (d, arom. Cq-OH, JP–C = 2.8 Hz), 154.29 (s, arom. Cq-OH),
137.64–122.21 (arom. C), 77.12 (s, OCH2Ph), 75.03 (s, OCH2Ph),
30.89 (s, ArCH2Ar). 31P{1H} NMR (121 MHz, CDCl3) d: 31.0 (s,
P(O)Ph2). Anal. Calc. for C80H66O6P2: C, 81.06; H, 5.61. Found: C,
80.89; H, 5.72%.
2.2.2. Synthesis of 5,17-bis(diphenylphosphino)-25,26,27,28-tetra-
hydroxycalix[4]arene – 2
Diphosphine 2 was obtained from 1 (0.577 g, 0.5 mmol) in 98%
yield (0.386 g). 1H NMR (300 MHz, CDCl3) d: 10.13 (s, 4H, OH),
7.35–7.24 (20H, arom. CH of PPh2), 7.04 (d, 4H, arom. CH of calix,
3JH–H = 7.5 Hz), 6.79 (s, 4H, arom. CH of calix), 6.66 (t, 2H, arom.
2.2.6. Synthesis of 5,17-bis(diphenylthiophosphinoyl)-25,26,27,28-
tetrabenzyloxycalix[4] arene – 6
To a solution of 1 (0.500 g, 0.43 mmol) in toluene (20 mL) was
added S8 (0.028 g, 0.11 mmol). The resulting solution was refluxed
for 10 min. Solvent evaporation under reduced pressure afforded
the bis-phosphine sulfide 6 as a white solid. Yield 100% (0.527 g).
1H NMR (300 MHz, CDCl3) d: 7.72–7.64 (8H, arom. CH), 7.52–7.46
(8H, arom. CH), 7.35–7.24 (8H, arom. CH), 7.33 (s, 4H, arom. CH
of calix), 7.15–7.09 (16H, arom. CH), 6.26 (t, 2H, arom. CH of calix,
3
CH of calix, JH–H = 7.5 Hz), 4.09 and 3.54 (AB spin system br, 8H,
ArCH2Ar). 13C{1H} NMR (75 MHz, CDCl3) d: 150.24 (s, arom. Cq-
OH), 148.43 (s, arom. Cq-OH), 137.89–122.75 (arom. C), 31.73 (s,
ArCH2Ar). 31P{1H} NMR (121 MHz, CDCl3) d: ꢂ6.1 (s, PPh2). Anal.
Calc. for C52H42O4P2: C, 78.77; H, 5.34. Found: C, 78.65; H, 5.15%.
3
3JH–H = 7.6 Hz), 5.97 (d, 4H, arom. CH of calix, JH–H = 7.6 Hz), 5.22
2.2.3. Synthesis of 5,17-bis(diphenylphosphinoyl)-25,26,27,28-tetra-
hydroxycalix[4]arene – 3
(s, 4H, CH2Ph), 4.64 (s, 4H, CH2Ph), 4.21 and 2.94 (AB spin system,
2
8H, ArCH2Ar, JH–H = 13.7 Hz). 13C{1H} NMR (75 MHz, CDCl3) d:
To a solution of 2 (0.100 g, 0.12 mmol) in CH2Cl2 (10 mL) was
added H2O2 (30% in water, 2 ml, 2.5 mmol). The resulting solution
was stirred at room temperature for 2 h. The mixture was then
treated with a mixture of CH2Cl2 (10 mL) and water (20 mL). After
extraction of the aqueous layer with CH2Cl2 (2 ꢁ 10 mL), the organ-
ic phases were combined. The resulting solution was washed with
water (2 ꢁ 10 mL), then dried over Na2SO4 and evaporated under
reduced pressure to afford the bis-phosphine oxide 3 as a white so-
lid. Yield 100% (0.104 g). 1H NMR (300 MHz, CDCl3) d: 10.15 (s, 4H,
OH), 7.67–7.60 (8H, arom. CH of P(O)Ph2), 7.56–7.52 (4H, arom. CH
of P(O)Ph2), 7.47–7.38 (12H, arom. CH of P(O)Ph2 and calix), 6.87
(d, 4H, arom. CH of calix, 3JH–H = 7.5 Hz), 6.67 (t, 2H, arom. CH of ca-
lix, 3JH–H = 7.5 Hz), 4.21 and 3.54 (AB spin system br, 8H, ArCH2Ar).
13C{1H} NMR (75 MHz, CDCl3) d: 152.85 (d, arom. Cq-OH,
4JP–C = 3.1 Hz), 147.96 (s, arom. Cq-OH), 133.43–122.90 (arom. C),
31.55 (s, ArCH2Ar). 31P{1H} NMR (121 MHz, CDCl3) d: 27.9
(s, P(O)Ph2). Anal. Calc. for C52H42O6P2: C, 75.72; H, 5.13. Found:
C, 75.61; H, 4.98%.
4
159.28 (d, arom. Cq-OH, JP–C = 3.1 Hz), 154.76 (s, arom. Cq-OH),
138.04–122.63 (arom. C), 77.63 (s, OCH2Ph), 75.48 (s, OCH2Ph),
31.39 (s, ArCH2Ar). 31P{1H} NMR (121 MHz, CDCl3) d: 42.8 (s,
P(S)Ph2). Anal. Calc. for C80H66O4S2P2: C, 78.92; H, 5.46. Found: C,
79.10; H, 5.34%.
2.2.7. Synthesis of P,P0-{5,17-bis(diphenylphosphino)-25,26,27,28-tetra-
hydroxycalix[4] arene}-bis[dichlorido(p-cymene)]ruthenium(II) – 7
To a solution of 2 (0.100 g, 0.12 mmol) in CH2Cl2 (10 mL) was
added a solution of [RuCl2(p-cymene)]2 (0.077 g, 0.12 mmol) in
CH2Cl2 (10 mL). The solution was stirred at room temperature for
0.5 h, then the reaction mixture was concentrated to ca. 2 mL be-
fore addition of n-hexane (50 mL) was added. The red product
was collected by filtration and dried under vacuum. Yield
(0.161 g, 92%). 1H NMR (300 MHz, CD2Cl2) d: 10.09 (s, 4H, OH),
7.82–7.77 (8H, arom. CH of PPh2), 7.58 (d, 4H, arom. CH of calix,
3JP–H = 10.0 Hz), 7.48–7.35 (12H, arom. CH of PPh2), 6.92 (d, 4H,
3
arom. CH of calix, JH–H = 7.6 Hz), 6.77 (t, 2H, arom. CH of calix,
2.2.4. Synthesis of 5,17-bis(diphenylthiophosphinoyl)-25,26,27,28-tetra-
hydroxycalix[4] arene – 4
3
3JH–H = 7.6 Hz), 5.15 (d, 4H, arom. CH of p-cymene, JH–H = 6.2 Hz),
3
5.05 (d, 4H, arom. CH of p-cymene, JH–H = 6.2 Hz), 4.23 and 3.51
To a solution of 2 (0.500 g, 0.63 mmol) in toluene (15 mL) was
added sulfur powder (S8, 0.040 g, 0.16 mmol). The resulting solu-
tion was refluxed for 10 min. The solvent was further evaporated
under reduced pressure to afford the bis-phosphine sulfide 4 as a
white solid. Yield 100% (0.540 g). 1H NMR (300 MHz, CDCl3) d:
10.13 (s, 4H, OH), 7.89–7.41 (24H, arom. CH of P(S)Ph2 and calix),
2
(AB spin system, 8H, ArCH2Ar, JH–H = 11.4 Hz), 2.61 (hept, 2H,
CH(CH3)2, 3JH–H = 6.9 Hz), 1.71 (s, 6H, CH3), 0.97 (d, 12H, CH(CH3)2,
3JH–H = 6.9 Hz). 13C{1H} NMR (75 MHz, CD2Cl2) d: 151.33 (s, arom.
Cq-OH), 148.32 (s, arom. Cq-OH), 135.56–122.39 (arom. C),
110.00 (s, arom. Cq of p-cymene), 95.97 (s, arom. Cq of p-cymene),
89.46 (s, arom. CH of p-cymene), 86.79 (s, arom. CH of p-cymene),
31.35 (s, ArCH2Ar), 30.08 (s, CH(CH3)2), 21.40 (s, CH(CH3)2), 17.11
(s, CH3). 31P{1H} NMR (121 MHz, CD2Cl2) d: 22.6 (s, PPh2). Anal.
Calc. for C72H70O4P2Ru2Cl4: C, 61.54; H, 5.02. Found: C, 61.32; H,
4.87%.
3
6.84 (d, 4H, arom. CH of calix, JH–H = 7.4 Hz), 6.69 (t, 2H, arom.
3
CH of calix, JH–H = 7.4 Hz), 4.49 and 3.52 (AB spin system br, 8H,
ArCH2Ar). 13C{1H} NMR (75 MHz, CDCl3) d: 152.60 (s, arom. Cq-
OH), 148.01 (s, arom. Cq-OH), 133.67–123.03 (arom. C), 31.60 (s,
ArCH2Ar). 31P{1H} NMR (121 MHz, CDCl3) d: 42.0 (s, P(S)Ph2). Anal.
Calc. for C52H42O4S2P2: C, 72.88; H, 4.94. Found: C, 72.75; H, 5.11%.
2.2.8. Synthesis of P,P0-{5,17-bis(diphenylphosphino)-25,26,27,28-
tetrahydroxycalix[4] arene}-bis[chlorido(1,5-cyclooctadiene)]-
iridium(I) – 8
2.2.5. Synthesis of 5,17-bis(diphenylphosphinoyl)-25,26,27,28-tetra-
benzyloxycalix[4]arene – 5
To a solution of 1 (0.576 g, 0.5 mmol) in CH2Cl2 (10 mL) was
added H2O2 (30% in water, 4 ml, 5.0 mmol). The resulting solution
To a solution of 2 (0.100 g, 0.12 mmol) in CH2Cl2 (10 mL) was
added a solution of [IrCl(COD)]2 (0.085 g, 0.12 mmol) in CH2Cl2

72
L. Monnereau et al. / Polyhedron 51 (2013) 70–74
(10 mL). The solution was stirred at room temperature for 0.5 h,
then the reaction mixture was concentrated to ca. 2 mL before
addition of n-hexane (50 mL) was added. The yellow product was
collected by filtration and dried under vacuum. Yield (0.173 g,
97%). 1H NMR (300 MHz, CD2Cl2) d: 10.18 (s, 4H, OH), 7.63–7.36
(24H, arom. CH of PPh2 and calix), 6.89 (d, 4H, arom. CH of calix,
2.4. General procedure for the catalytic hydrogenation
The hydrogenation experiments were carried out in a glass-
lined, 100-mL stainless steel autoclave containing a magnetic stir-
ring bar. In a typical run, the autoclave was charged successively
under nitrogen with bis-rhodium complex 9 (0.006 g, 0.005 mmol,
1 mol% of Rh) dissolved in the solvent (5 mL of THF) and substrate
(1.0 mmol). Once closed, the autoclave was flushed twice with
hydrogen, then pressurised. At the end of the catalytic run, the
autoclave was depressurized and the resulting solution was passed
through a Millipore filter and analyzed by GC (Varian 3900 gas
3
3JH–H = 7.4 Hz), 6.75 (t, 2H, arom. CH of calix, JH–H = 7.4 Hz), 5.13
(s br, 4H, CH of COD), 4.25 and 3.57 (AB spin system, 8H, ArCH2Ar,
2JH–H = 13.1 Hz), 2.64 (s br, 4H, CH of COD), 2.64–2.11 (8H, CH2 of
COD), 1.89–1.84 (4H, CH2 of COD), 1.58–1.54 (4H, CH2 of COD).
13C{1H} NMR (75 MHz, CD2Cl2) d: 151.64 (s, arom. Cq-OH),
148.44 (s, arom. Cq-OH), 137.05–122.42 (arom. C), 93.75 (d, CH
chromatograph equipped with
a WCOT fused-silica column:
2
of COD, JP–C = 14.0 Hz), 33.31 (s, CH2 of COD), 31.38 (s, ArCH2Ar),
25 m ꢁ 0.25 mm).
29.51 (s, CH2 of COD). 31P{1H} NMR (121 MHz, CD2Cl2) d: 21.1 (s,
PPh2). Anal. Calc. for C68H66O4P2Ir2Cl2: C, 55.77; H, 4.54. Found: C,
55.84; H, 4.36%.
3. Results and discussion
Treatment of the bis(diphenylphosphino)-tetrabenzyloxyca-
lix[4]arene 1 with AlCl3 in toluene led quantitatively to the tetra-
hydroxy-calixarene 2. The oxidation of 2 with H2O2 gave the
bis-(phosphine oxide) 3, while reaction of 2 with S8 in toluene
resulted in the bis-(phosphine sulfide) 4. Another route leading
to 3 consisted in forming first the bis-phosphine oxide 5, then
removing the protecting benzyl groups with AlCl3. A similar alter-
native approach was applied for the synthesis of 4 (Scheme 1).
While the 1H NMR (CDCl3) spectra of calixarenes 1, 5 and 6 each
show a well-resolved AB pattern for the ArCH2Ar groups (dA–
dB = 1.32, 1.30 and 1.27, respectively), indicative of a calixarene
fixed in the cone conformation, that of the hydroxy calixarenes 2,
3, and 4, show two broad signals for the methylenic protons (dA–
dB = 0.55, 0.67 and 0.97, respectively). The large methylene signals
are likely to reflect rapid trans annular rotation of the phenolic
rings of the tetrahydroxy-calixarenes 2–4, a phenomenon that is
well documented [22,23]. It is noteworthy that for all three com-
pounds the ArCH2Ar carbon atoms appear as a singlet at ca.
31.5 ppm in the corresponding 13C NMR spectra.
2.2.9. Synthesis of P,P0-{5,17-bis(diphenylphosphino)-25,26,27,28-tetra-
hydroxycalix[4] arene}-bis[chlorido(1,5-cyclooctadiene)]rhodium(I) – 9
To a solution of 2 (0.100 g, 0.12 mmol) in CH2Cl2 (10 mL) was
added a solution of [RhCl(COD)]2 (0.062 g, 0.12 mmol) in CH2Cl2
(10 mL). The solution was stirred at room temperature for 0.5 h,
then the reaction mixture was concentrated to ca. 2 before addition
of n-hexane (50 mL) was added. The yellow product was collected
by filtration and dried under vacuum. Yield (0.155 g, 95%). 1H NMR
(300 MHz, CDCl3) d: 10.34 (s, 4H, OH), 7.79 (d, 4H, arom. CH of
3
PPh2, JH–H = 10.1 Hz), 7.75–7.7.60 (8H, arom. CH of PPh2), 7.49–
7.36 (8H, arom. CH of PPh2 and calix), 7.26–7.02 (4H, arom. CH
3
of PPh2), 6.93 (d, 4H, arom. CH of calix, JH–H = 7.5 Hz), 6.77 (t,
3
2H, arom. CH of calix, JH–H = 7.5 Hz), 5.62 (s br, 4H, CH of COD),
4.25 and 3.54 (AB spin system, 8H, ArCH2Ar, 2J = 12.7 Hz), 3.07 (s
br, 4H, CH of COD), 2.52–2.26 (8H, CH2 of COD), 2.08–2.01 (4H,
CH2 of COD), 1.91–1.82 (4H, CH2 of COD). 13C{1H} NMR (75 MHz,
CDCl3) d: 151.69 (s, arom. Cq-OH), 148.14 (s, arom. Cq-OH),
2
137.10–122.88 (arom. C), 104.96 (d, CH of COD, JP–C = 12.7 Hz),
2
78.73 (d, CH of COD, JP–C = 12.7 Hz), 33.13 (s, CH2 of COD), 31.65
Crystals of 3 suitable for X-ray diffraction formed readily upon
diffusion of hexane into a dichloromethane solution of the bis-
phosphine oxide. The molecule crystallises in the orthorhombic
system, space group Pbca. In the solid state (Fig. 1), the calix[4]ar-
ene cavity adopts a flattened cone conformation, with interplanar
angles between opposite phenoxy rings of 28.4° and 78.6°, respec-
tively. The separations between the aromatic carbon atoms of
opposite phenolic rings are 6.54 and 9.67 Å, respectively. The
P@O vectors are both pushed away from the axis of the cavity,
the distance between the two phosphorus atoms being 12.691 Å.
It should be mentioned here that the vast majority of tetra-hydro-
xy-calix[4]arenes reported in the literature adopt, in the solid state,
an almost perfect cone shape owing to the formation of a stable
cyclic H-bond network formed by the four hydroxyl groups
[24,25]. This is not the case in 3, possibly because of the capacity
of two hydroxyl groups to form stronger hydrogen bonds with
phosphoryl groups. Careful examination of the structure revealed
that indeed each calixarene is linked to two other calixarenes via
hydrogen bonds involving the phosphoryl groups as well as two
of the four hydroxyl groups, thereby generating a polymeric chain.
Thus, in the resulting supramolecular structure, each calixarene
link is attached through two points to the calixarene that precedes
it and also through two points to that which follows it (Fig. 2).
In order to evaluate the capacity of diphosphine 2 to form che-
late complexes, this ligand was reacted with the following com-
plexes, all suitable for coordinating two phosphine ligands:
(s, CH2 of COD), 30.92 (s, ArCH2Ar). 31P{1H} NMR (121 MHz, CDCl3)
d: 30.5 (d, PPh2, 1JRh–P = 149.6 Hz). Anal. Calc. for C68H66O4P2Rh2Cl2:
C, 63.51; H, 5.17. Found: C, 63.67; H, 5.01%.
2.3. Crystallographic analysis
Single, colourless crystals of 3 suitable for X-ray diffraction
were obtained by slow diffusion of hexane into a CH2Cl2 solution
of the bis-(phosphine oxide) at room temperature. Formula of
the crystals:
C52H42O6P4, Mr = 824.80, orthorhombic, Pbca,
a = 17.5363(7),
b = 24.5314(9), c = 19.1121(8) Å, d = 90.00,
d = 90.00, d = 90.00°, V = 8221.8(6) Å3, Z = 8, Dx = 1.333 Mg mꢂ3, d
(Mo
Ka
) = 0.71073 Å,
l
= 0.159 mmꢂ1
,
F(000) = 3456,
T = 110(2) K. The sample (0.25 ꢁ 0.20 ꢁ 0.20 mm) was mounted
on an Oxford Diffraction Xcalibur Saphir 3 diffractometer with
graphite monochromatized Mo K
a radiation. The data collection
(2hmax = 27°, omega scan frames via 0.7° omega rotation and 30 s
per frame, range HKL: H ꢂ22,21 K ꢂ31,26 L ꢂ18,24) gave 57600
reflections. The data led to 8957 independent reflections from
which 3840 with I > 2.0 > (I) were observed. The structure was
solved with SIR-97 [20], which revealed the non-hydrogen atoms
of the molecule. After anisotropic refinement, all the hydrogen
atoms are found with a Fourier Difference. The whole structure
was refined with SHELXL97 [21] by the fullmatrix least-square tech-
niques (use of F square magnitude; x, y, z, bij for P, C and O atoms, x,
y, z in riding mode for H atoms; 541 variables and 3840 observa-
[PtCl2(PhCN)2],
(COD = 1,5-cyclooctadiene), [RuCl(p-cymene)(THF)2]BF4, [Rh(COD)
(THF)2]BF4, [RhCl(CO)2]2, [Pd(SMe2)4](BF4)2, and [Ni(COD)(g5
C5H5)]BF4. Each reaction led to a mixture of complexes, mainly
[Pd(g
3-allyl)(acetone)2]PF6,
[PdCl2(COD)]
tions with I > 2.0
P = (Fo2 + 2Fc2)/3 with the resulting R = 0.0493, RW = 0.1123 and
SW = 0.822,
< 0.649 e Åꢂ3
r(I); calc w = 1/[r
2(Fo2) + (0.0619P)2] where
-
D
q
.

L. Monnereau et al. / Polyhedron 51 (2013) 70–74
73
PPh2
Ph2P
PPh2
Ph2P
AlCl3
toluene
OBn
OBn
BnO
BnO
OH
OH
HO
HO
1
2
i or ii
i or ii
X
X
X
X
PPh2
PPh2
Ph2P
Ph2P
AlCl3
toluene
OBn
OH
OBn
OH
BnO
HO
HO
BnO
5
6
X = O
X = S
3
X = O
4 X = S
Scheme 1. Synthesis of diphosphine 2, bis-(phosphine oxide) 3 and bis-(phosphine sulfide) 4: i: H2O2 in CH2Cl2/H2O; ii: S8 in toluene.
Fig. 1. ORTEP drawing of bis-(phosphine oxide) 3. Displacement ellipsoids are drawn at the 50% probability level. Selected bond lengths (Å) and angles (°): P(1)–C(4) 1.792(3),
P(1)–O(5) 1.4817(18), P(2)–C(17) 1.805(3), P(2)–O(6) 1.477(2), O(5)–P(1)–C(4) 114.87(11), O(5)–P(1)–C(35) 111.77(12), C(4)–P(1)–C(35) 106.23(13), O(5)–P(1)–C(29)
109.48(12), C(4)–P(1)–C(29) 106.29(12), C(35)–P(1)–C(29) 107.83(12), O(6)–P(2)–C(41) 114.32(14), O(6)–P(2)–C(17) 112.75(13), C(41)–P(2)–C(17) 107.61(13), O(6)–P(2)–
C(47) 111.34(13), C(41)–P(2)–C(47) 103.37(14), C(17)–P(2)–C(47) 106.78(13).
Fig. 2. Part of the polymer chain generated by 3 in the solid state.

74
L. Monnereau et al. / Polyhedron 51 (2013) 70–74
cyclooctene was completed after 4 h (Table 1, entries 5 and 7),
2
while pentyne was converted into pentane in 24 h (Table 1, entry
8). The observed activities are not unusual for rhodium-phosphine
complexes.
[RuCl2(p-cymene)]2
CH2Cl2
[MCl(cod)]2
CH2Cl2
4. Conclusion
We have described the synthesis of 5,17-bis(diphenylphos-
phino)-25,26,27,28-tetrahydroxycalix[4]arene (2), a rare example
of diphosphine based on a tetra-hydroxy-calixarene skeleton, and
of the corresponding bis-(phosphine oxide) 3 and bis-(phosphine
sulfide) 4. All three calixarenes display conformational mobility
in solution due to easy trans-annular rotation of the phenolic rings.
An X-ray structure determination revealed that in the solid state
the phosphorylated compound 3 adopts a pinched rather than a
‘‘pure’’ cone conformation, both phosphoryl groups interacting
with hydroxyl groups of neighbouring calixarenes so as to result
in a polymeric chain structure. Diphosphine 2 is not suited for
forming chelate complexes, but forms readily dinuclear complexes.
Cl
Cl
Cl
Ru
Ru
Cl
PPh2
Ph2P
M
M
Cl
Cl
PPh2
Ph2P
OH
OH
HO
HO
7
OH
OH
HO
HO
Acknowledgement
8 M = Ir
9 M = Rh
This work was supported by the University of Strasbourg (grant
to L.M.).
Scheme 2. Synthesis of the dinuclear complexes 7–9.
Appendix A. Supplementary data
Table 1
Catalytic hydrogenation using bis-rhodium complex 9.a
CCDC 680936 contains the supplementary crystallographic data
for 3. These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Entry Substrate
Time
(h)
P(H2)
(bar)
Conversion into
alkane (%)
1
2
3
1
1
1
1
5
5
59.1
100
100
C6H13
Ph
O
References
4
5
1
4
5
5
44.5
100
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q
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The bis-rhodium complex 9 was assessed in catalytic hydroge-
nation of alkenes and alkyne into alkanes (Table 1). Using 1 mol% of
rhodium under a H2 pressure of 5 bar resulted in full conversion
after 1 h of alkyl substituted olefins (1-octene and allylbenzyl
ether; Table 1, entries 2 and 3). Hydrogenation of styrene and