Monophosphanylcalix[6]arene ligands: Synthesis characterization, complexation, and their use in catalysis

Article abstract of DOI:10.1002/ejic.200500673

Novel phosphanylcalix[6]arenes having mono-O-diphenylphosphanylmethyl (3) and mono-O-(4-diphenylphosphanylphenyl)methyl substituents (5) have been synthesized. The structures of these monophosphanylcalix[6]arenes were determined by NMR spectroscopy, mass spectrometry, and X-ray crystal structure analysis. The X-ray structure reveals that 3 adopts a flattened 1,2,3-alternate conformation in the crystalline state, while the NMR spectra show that 3 and 5 have a cone conformation in solution. Structure optimization and energy calculations for 3 and 5 at the B3LYP/LANL2DZ-CONFLEX5/MMFF94s level of theory show that the cone conformation is slightly more stable than the 1,2,3-alternate conformation by 0.36 kcal mol^-1 for 3 and 0.96 kcal mol^-1 for 5. Complexation of 3 with [PtCl₂(COD)] and [Rh(COD) ₂]BF₄ gives cis-coordinated [PtCl₂(3) ₂] and [Rh(COD)(3)₂]BF₄, respectively. The X-ray analysis of [PtCl₂(3)₂] shows that 3 adopts a cone conformation upon complexation. Combination of 3 and 5 with [Rh(COD) ₂]BF₄ provides an active catalyst for the hydroformylation of a variety of terminal alkenes. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200500673

FULL PAPER
DOI: 10.1002/ejic.200500673
Monophosphanylcalix[6]arene Ligands: Synthesis Characterization,
Complexation, and Their Use in Catalysis
Yasushi Obora,[a] Yun Kui Liu,[a] Sho Kubouchi,[a] Makoto Tokunaga,[a] and
Yasushi Tsuji*[a]
Keywords: Calixarenes / Heterogeneous catalysis / Phosphanes / Platinum / Rhodium
Novel phosphanylcalix[6]arenes having mono-O-diphenyl-
phosphanylmethyl (3) and mono-O-(4-diphenylphosphanyl-
phenyl)methyl substituents (5) have been synthesized. The
structures of these monophosphanylcalix[6]arenes were de-
termined by NMR spectroscopy, mass spectrometry, and X-
ray crystal structure analysis. The X-ray structure reveals
that 3 adopts a flattened 1,2,3-alternate conformation in the
crystalline state, while the NMR spectra show that 3 and 5
have a cone conformation in solution. Structure optimization
and energy calculations for 3 and 5 at the B3LYP/LANL2DZ-
CONFLEX5/MMFF94s level of theory show that the cone
conformation is slightly more stable than the 1,2,3-alternate
conformation by 0.36 kcalmol–1 for 3 and 0.96 kcalmol–1 for
5. Complexation of 3 with [PtCl2(COD)] and [Rh(COD)2]BF4
gives cis-coordinated [PtCl2(3)2] and [Rh(COD)(3)2]BF4,
respectively. The X-ray analysis of [PtCl2(3)2] shows that 3
adopts a cone conformation upon complexation. Combina-
tion of 3 and 5 with [Rh(COD)2]BF4 provides an active cata-
lyst for the hydroformylation of a variety of terminal alkenes.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
ene,[6b] and an RuII complex of a tetrakis(diphenylphos-
phanylmethyl)calix[4]arene.[6c] Calix[6]arenes having larger
cavities generally display more flexible and variable confor-
mations[7] than calix[4]arenes. Therefore, the chemistry of
phosphanylcalix[6]arenes[8] is essentially unexplored owing
to their intricacy. We recently synthesized 1,3,5-triphos-
phanylcalix[6]arene, which functions as a tripodal phos-
phane ligand to afford novel, capsule-shaped IrI and RhI
complexes.[9]
In the present study, we describe the synthesis and char-
acterization of novel phosphanylcalix[6]arenes having
mono-O-diphenylphosphanylmethyl (3) and mono-O-(4-di-
phenylphosphanylphenyl)methyl substituents (5) as the first
examples of a calix[6]arene moiety bearing monodentate
phosphane ligands.[10] The monodentate phosphanes are an
important class of ligands in transition-metal-catalyzed re-
actions.[3,11] Furthermore, we have synthesized PtII and RhI
complexes of 3, and found that the RhI complexes of 3 and
5 are active catalysts in the hydroformylation of terminal
alkenes.
Introduction
Calixarenes are macrocyclic compounds having well-de-
fined cavities, and a number of synthetic procedures for
their selective functionalization have been developed.[1] In
particular, phosphanylcalixarenes,[2] namely phosphanes
bearing calixarene moieties, have received considerable at-
tention. Phosphane ligands in general play an important
role in transition-metal-catalyzed reactions, and a wide vari-
ety of phosphanes have been prepared to realize high cata-
lytic activity and selectivity.[3,4] The phosphanylcalixarenes
are attractive ligands since they integrate the strong coordi-
nation ability of phosphanes and the unique cavity of the
calixarenes to create a spatially confined environment upon
complexation with transitional metals.[2]
As far as the size of the cavity is concerned, major atten-
tion has been paid to phosphanylcalix[4]arenes[5] due to
their rigid conformations. As for the phosphanylcalix[4]ar-
enes, we have reported PtII and PdII complexes of a bis(di-
phenylphosphanyl)calix[4]arene,[6a] solid-state and solution
structures of
a
tetrakis(diphenylphosphanyl)calix[4]ar-
Results and Discussion
The monophosphanylcalix[6]arene ligands 3 and 5 were
prepared as shown in Scheme 1. According to the reported
synthetic procedure for phosphanylcalix[4]arenes[5n,12] and
triphosphanylcalix[6]arenes,[9] 3 was prepared as follows.
Reaction of 1[13] with Ph2P(O)CH2OTs[14] with NaH as a
base, in toluene at 90 °C for 2 d, gave the phosphane oxide
2 in 95% yield. Reduction of 2 was carried out with PhSiH3
[a] Catalysis Research Center and Division of Chemistry, Graduate
School of Science Hokkaido University, CREST, Japan Science
and Technology Agency (JST),
Sapporo 001-0021, Japan
Fax: +81-11-706-9156
E-mail: tsuji@cat.hokudai.ac.jp
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
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Monophosphanylcalix[6]arene Ligands
FULL PAPER
in toluene under reflux to afford 3 in 90% yield. With re- 0.2162 Å) are 84.3(1)°, 137.2(1)°, 66.9(1)°, 73.4(1)°,
gard to the synthesis of 5, the corresponding phosphane 136.2(1)°, and 68.7(1)°, respectively. This structure can also
oxide (4) was prepared from 1, Ph2P(O)C6H4CH2Br,[15] and be designated as a (u,uo,u,d,do,d) conformation, as sug-
NaH in DMF at 50 °C for 20 h by modifying the reported gested by Gutsche.[18] Similar 1,2,3-alternate conformations
procedure for mono-O-benzylation of calix[6]arenes.[16] The in the crystalline state have also been reported for several
desired phosphane (5) was obtained in 82% yield after re- hexasubstituted calix[6]arene derivatives.[19]
duction of 4 with PhSiH3.
Figure 1. ORTEP drawing of the molecular structure of 3 with
thermal ellipsoids at 50% probability levels. Hydrogen atoms have
been omitted for clarity.
Table 1. Selected bond lengths [Å] and angles [°] for 3.
P(1)–C(1)
1.863(6)
1.420(6)
1.436(6)
1.413(7)
102.2(2)
P(1)–C(7)
1.825(6)
1.431(7)
1.440(6)
1.433(7)
105.8(3)
O(1)–C(1)
O(3)–C(3)
O(5)–C(5)
C(7)–P(1)–C(8)
O(2)–C(2)
O(4)–C(4)
O(6)–C(6)
P(1)–C(1)–O(1)
To elucidate the structures of 3 and 5 in solution, 1H and
13C{1H} NMR spectra of 3 and 5 were measured in CDCl3
1
at 25 °C. All the H and 13C resonances were completely
assigned by means of HMBC[20] 2D NMR spectroscopy. In
solution, both compounds 3 and 5 show quite similar NMR
Scheme 1.
spectra in terms of the conformation of calix[6]arene moie-
1
These phosphane compounds (3 and 5) were charac- ties. The H NMR spectrum of 3 exhibits axial bridging
terized by means of NMR spectroscopy, mass spectrometry, methylene proton resonances as three doublets at δ = 4.03,
elemental analysis, and X-ray crystal structure analysis. The 4.19, and 4.35 ppm in a 1:1:1 ratio, and the corresponding
31P{1H} NMR spectra (in CDCl3) of 3 and 5 at 25 °C dis- equatorial proton resonances as three doublets at δ = 3.85,
play single resonances at δ = –16.5 and –5.6 ppm assignable 3.70, and 3.48 ppm in a 1:1:1 ratio, with geminal couplings
1
to alkyldiaryl- and triarylphosphanes, respectively. The ESI (J = 14–15 Hz). Similarly, the H NMR spectrum of 5 dis-
or FD mass spectra of 3 and 5 show peaks at m/z = 1264 [M plays signals of three axial bridging methylene protons at δ
+ Na]+ (for 3) and 1318 [M+] (for 5). The X-ray structure of = 4.04, 4.16, and 4.43 ppm and of three equatorial protons
3 is shown in Figure 1. The crystallographic data are listed at δ = 3.81, 3.68, and 3.51 ppm as doublets. With regard to
in the Experimental Section and selected atom distances the bridging methylene resonances in the 1H NMR spectra,
and bond angles of 3 in Table 1. The X-ray structure shows the difference of the chemical shift (∆δ) between the axial
that 3 adopts a 1,2,3-alternate conformation in which three and the equatorial pairs is dependent on the orientation of
pairs of diametrically opposite phenyl rings (A vs. D, B vs. the two adjacent aromatic rings.[21] The ∆δ values (0.87,
E, and C vs. F) orient anti to each other.[17] Four of these 0.49, and 0.18 ppm for 3 and 0.92, 0.48, and 0.23 ppm for 5)
aromatic rings (A, C, D, and F) almost stand up in pinched are quite similar to the values reported for mono-O-benzyl-
positions whereas the other two aromatic rings (B and E) substituted calix[6]arene (0.94, 0.50, and 0.21 ppm), which
splay outwards in flattened positions. Thus, the dihedral was assigned a cone conformation in solution.[22] Further-
angles between the aromatic rings (A–F) and the calixarene more, the tert-butyl protons appear as four singlet peaks in
reference plane (the average plane defined by the six bridg- a 1:1:2:2 ratio (δ = 0.92, 1.27, 1.06, and 1.30 ppm for 3 and
ing methylene carbon atoms; the maximum deviation is δ = 0.97, 1.23, 1.02, and 1.24 ppm for 5), and the methoxy
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Y. Obora, Y. K. Liu, S. Kubouchi, M. Tokunaga, Y. Tsuji
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protons as three singlet peaks in a 1:2:2 ratio (δ = 2.81,
2.50, and 3.26 ppm for 3 and δ = 2.76, 2.49, and 3.22 ppm
for 5) in the 1H NMR spectra. It is well known that a signal
arising from the bridging methylene carbon atoms (Ar-
CH2-Ar) appears at δ Ϸ 31 ppm in the 13C{1H} NMR spec-
trum when two adjacent aryl rings are in the syn orienta-
tion, and close to δ = 37 ppm for the anti orientation.[22,23]
Here, the bridging methylene carbon resonances appear at
δ = 30.38, 30.48, and 30.64 ppm for 3 and δ = 30.42, 30.76,
and 30.80 ppm for 5 in 1:1:1 ratios, with no methylene reso-
nances at δ = 36–38 ppm. The ROESY spectrum of 3 at
25 °C shows that all the equatorial protons have ROE corre-
lations with one of the aromatic protons of the calixarene
moiety; no ROE correlation was observed between the axial
protons and the aromatic protons (see Figure S2 in the Sup-
porting Information). Variable-temperature 13C{1H}NMR
spectra of 3 in the range from –50 to 25 °C showed that the
bridging methylene carbon signals (δ = 29–31 ppm) re-
1
mained virtually unchanged, whereas the H NMR spectra
showed that two pairs of bridging methylene doublets (δ
= 4.19/3.70 and 4.03/3.85 ppm) became slightly broadened,
while the remaining pair (δ = 4.35/3.48 ppm) remained as a
sharp peak on lowering the temperature to –50 °C. All these
NMR spectroscopic data clearly indicate that 3 and 5 adopt
a cone conformation[22–24] in solution.[25]
The CPMAS solid-state 13C{1H} NMR spectra of 3
(Figure 2) and 5 (as a powder, not a single crystal) show
comparable chemical shifts to the solution spectra, al-
though the resonances in the solid state are considerably
broader (∆ν1/2 = 50–180 Hz). The diagnostic bridging meth-
Figure 2. 13C{1H} NMR spectra of 3 at 25 °C: (a) measured in
CD2Cl2; (b) measured in the solid state (CPMAS). *ssb: spinning
side-band.
ylene carbon resonances appear at δ Ϸ 30.5 ppm (∆ν1/2
=
172 Hz) for 3 and δ Ϸ 31.1 ppm (for 5), rather than at δ =
36–38 ppm, thus indicating that 3 and 5 have the same cone
structure in the solid state as in solution.
The structural differences between the solution (cone),
powder (cone), and the single crystal (1,2,3-alternate) sug- than the cone conformation. This result can explain why no
gest that the energy difference between these conformations 1,3,5-alternate conformations were observed for 3 and 5
is very small. Thus, an MO calculation was carried out for and that facile conformational interconversion between the
the 1,2,3-alternate (Figure 3a for 3; Figure 3d for 5) and the 1,2,3-alternate and the cone takes place to afford the 1,2,3-
cone conformations (Figure 3b for 3; Figure 3e for 5) as alternate conformation in the crystal structure, possibly by
well as a common 1,3,5-alternate[18] conformation (Fig- a preferential crystallization of this conformation.[30]
ure 3c for 3; Figure 3f for 5). In each conformation, confor-
The 13C NMR chemical shifts of 3 were calculated by
mational analysis of 3 and 5 was carried out by CON- the GIAO (Gauge-Independent Atomic Orbital)[31] method
FLEX5[26]/MMFF94s[27] to find the lowest-energy struc- at the HF/6-31G(d) level of theory for the optimized cone
ture. The structures were then further optimized by DFT (Figure 3b) and the 1,2,3-alternate (Figure 3a) structures.
calculations at the B3LYP[28]/LANL2DZ[29] level. The opti- As shown in Table 2 and Figure 4, the calculated chemical
mized structures are shown in Figure 3a–f, which reproduce shifts of the cone structure are in good correlation with the
the characteristic structural features: (u,uo,u,d,do,d) for the values observed in CD2Cl2 (r2 = 0.996), thereby indicating
1,2,3-alternate (Figure 3a and d), (u,u,u,u,u,u) for the cone that the calculation is reliable, although the calculated val-
(Figure 3b and e), and (u,di,u,d,ui,d)[18] for the 1,3,5-alter- ues are smaller than the observed ones by 1.5–5 ppm. It is
nate conformation (Figure 3c and f). The energy calcula- noteworthy that among the six bridging methylene carbon
tions on these optimized structures at the same level atoms of the 1,2,3-altenate structure, the calculated chemi-
(B3LYP/LANL2DZ) revealed that the energy difference be- cal shifts of the four carbon atoms (δ = 28.04, 28.44, 28.45,
tween the 1,2,3-alternate and the cone conformations is and 28.46 ppm) of the syn orientation are definitely smaller
very small: the latter is slightly more stable than the former than those of the two carbon atoms of the anti orientation
but only by 0.36 (for 3) and 0.96 kcalmol–1 (for 5). How- (δ = 32.40 and 32.42 ppm). Such explicit differences would
ever, the 1,3,5-alternate conformation is considerably less warrant the aforementioned diagnostic bridging methylene
stable (11.93 kcalmol–1 for 3 and 12.67 kcalmol–1 for 5) carbon resonances of the syn and anti orientations.
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Monophosphanylcalix[6]arene Ligands
FULL PAPER
Figure 3. Conformers and optimized structures (B3LYP/LANL2DZ–CONFLEX5/MMFF94s) of 3 [(a) 1,2,3-alternate, (b) cone, (c) 1,3,5-
alternate] and 5 [(d) 1,2,3-alternate, (e) cone, (f) 1,3,5-alternate].
Table 2. GIAO calculation of 13C NMR chemical shifts [ppm] of 3
at the HF/6-31G(d) level for the cone and the 1,2,3-alternate con-
formers.
Cone
1,2,3-Alternate
Calculated
Calculated Experimental[a]
Ar–CH2–Ar
(CH3)3C–Ar
27.24 (syn)
28.65 (syn)
29.05 (syn)
28.12
28.23
28.68
28.69
31.21
31.28
31.43
30.81 (–3.57)
30.44 (–1.79)
30.53 (–1.48)
31.48 (–3.36)
31.38 (–3.15)
31.68 (–3.00)
31.63 (–2.94)
34.34 (–3.13)
34.34 (–3.06)
34.43 (–3.00)
34.43 (–3.00)
60.20 (–5.02)
60.24 (–4.48)
60.37 (–4.51)
75.02 (–1.84)
28.04 (syn), 28.44 (syn)
28.45 (syn), 28.46 (syn)
32.40 (anti), 32.42 (anti)
28.32, 28.33, 28.36
28.46, 28.68, 28.72
Figure 4. Correlation plots of the calculated vs. experimental 13C
NMR chemical shifts for the cone conformer.
(CH3)3C–Ar
31.38, 31.40, 31.41
31.43, 31.47, 31.65
Preparation of Platinum(II) and Rhodium(I) Complexes of 3
PtII and RhI complexes of 3 were prepared. Compound
3 (2 equiv.) was treated with [PtCl2(COD)] (COD = 1,5-
cyclooctadiene) to afford [PtCl2(3)2] in 78% yield [Equa-
tion (1)]. Characterization of [PtCl2(3)2] was performed by
NMR spectroscopy, mass spectrometry, elemental analysis,
and X-ray crystal structure analysis. The ESI mass spec-
trum of [PtCl2(3)2] exhibits an intense signal for [M + Na]+
31.43
55.18
55.76
55.86
CH3O–Ar
54.09, 54.20
55.09, 55.31
55.33
O–CH2–PPh2
73.18
70.80
[a] In CD2Cl2 at 25 °C (Figure 2a). The figures in parentheses show
the difference between the calculated and experimental chemical
shifts.
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Y. Obora, Y. K. Liu, S. Kubouchi, M. Tokunaga, Y. Tsuji
FULL PAPER
(m/z = 2770). The structure of [PtCl2(3)2] was unequivocally data indicate that the calixarene moieties of [PtCl2(3)2] re-
confirmed by X-ray diffraction. Figure 5 shows the molecu- main in the cone conformation in solution, as is also the
lar structure of [PtCl2(3)2]. The crystal data and selected case in the crystalline state (Figure 5). The 31P{1H} NMR
bond lengths and angles are summarized in the Experimen- spectrum displays a singlet peak at δ = 6.0 ppm with a 1JPt,P
tal Section and Table 3, respectively. In contrast to the coupling constant of 3611 Hz, which indicates the cis coor-
structure of 3 (Figure 1), the two calix[6]arene moieties in dination of the phosphane ligand.[5a,34] When the cis com-
[PtCl2(3)2] adopt a cone conformation. The platinum atom plex was heated at 60 °C for 24 h, no cis/trans isomeriza-
is cis-coordinated by two phosphane groups and the P1– tion[35] was observed.
Pt–P2 bond angle is 97.6(5)°, which is comparable to the
Treatment of 3 with [Rh(COD)2]BF4 in CH2Cl2 afforded
value of 98.1(3)° found in cis-[PtCl2(PMePh2)2].[32] The [Rh(COD)(3)2]BF4 in 68% yield [Equation (2)]. The ESI
Cl(1)–Pt(1)–P(1) and Cl(2)–Pt(1)–P(2) angles are 170.82 mass spectrum of this complex shows an intense peak at
– +
1
(5)° and 172.15 (6)°, respectively. Thus, the geometry of the m/z = 2694 ([M – BF4 ] ). In the H and 13C{1H} NMR
platinum center is approximately square-planar with a spectra of [Rh(COD)(3)2]BF4 (see Experimental Section),
slightly tetrahedral distortion. The Pt–P bond lengths the resonances for the bridging methylene protons and car-
[2.255(1) and 2.247(2) Å] and the Pt–Cl bond lengths bon atoms and the tert-butyl and methoxy protons indicate
[2.359(2) and 2.349(1) Å] are similar to those in cis- that the calix[6]arene moieties also maintain the cone con-
[PtCl2(PMePh2)2][32] and other phosphanylcalixarene-based formation in the complex. The 31P NMR spectrum of the
PtII complexes.[33]
complex shows a resonance at δ = 20.8 ppm (1JRh,P
=
141 Hz), which is consistent with a cis-planar structure as
was reported for [Rh(COD)(DPPB)]BF4 [DPPB = 1,4-
bis(diphenylphosphanyl)butane; δ =23.5 ppm (1JRh–P
=
144 Hz)].[36]
(1)
(2)
Hydroformylation Experiments
It is known that (phosphanylcalix[4]arene)rhodium com-
plexes have been found to be active catalysts for the hydro-
formylation of olefins.[5c,5g,5k,5n,5o] Phosphanylcalix[6]arenes
have a larger cavity than phosphanylcalix[4]arenes; there-
fore, in order to examine the catalytic performance (cata-
lytic activity and regioselectivity) of the novel monophos-
phanylcalix[6]arene ligands 3 and 5, RhI-catalyzed hydro-
formylations of four different terminal olefins were exam-
ined [Equation (3) and Table 4]. The hydroformylation reac-
tions were carried out with a 1:1 mixture of CO/H2 (10 atm)
in the presence of [Rh(COD)2]BF4 combined with 3 or 5
(olefin/Rh/P ratio = 2000:1:4) in benzene at 70 °C. When 1-
hexene was employed as substrate, 1-heptanal (linear) and
2-methylhexanal (branched) were formed in 79% (with 3)
and 85% (with 5) total yields (Entries 1 and 2). The present
catalysts also show high activity in hydroformylation of sty-
rene to afford the branched aldehyde as the major product
Figure 5. ORTEP drawing of [PtCl2(3)2] with thermal ellipsoids at
50% probability levels. Hydrogen atoms have been omitted for clar-
ity.
Table 3. Selected bond lengths [Å] and angles [°] for [PtCl2(3)2].
Pt(1)–P(1)
Pt(1)–Cl(1)
P(1)–C(1)
O(1)–C(1)
P(1)–Pt(1)–P(2)
Cl(1)–Pt(1)–P(1)
O(1)–C(1)–P(1)
2.255(1)
2.350(2)
1.847(7)
1.430(8)
97.57(5)
170.82(6)
108.9(3)
Pt(1)–P(2)
Pt(1)–Cl(2)
P(2)–C(2)
O(7)–C(2)
Cl(1)–Pt(1)–Cl(2)
Cl(2)–Pt(1)–P(2)
O(7)–C(2)–P(2)
2.247(2)
2.359(2)
1.857(7)
1.424(7)
87.28(6)
172.15(6)
109.0(4)
1
In solution, the H NMR spectrum of [PtCl2(3)2] shows (Entries 3 and 4). These regioselectivities (linear/branched
the bridging methylene protons as five distinct doublets ratios) are similar to those reported with phosphanylcalix[4]-
with geminal couplings of 15 Hz; the other doublet is over- arene ligands[5c,5g,5k,5o,5n] and conventional phosphanes.[37]
lapped by the methoxy proton resonances. The tert-butyl In the hydroformylation of vinyl acetate and vinyl benzoate,
protons appear as four singlets in a 1:1:2:2 ratio and the the rhodium catalyst with 3 shows a better catalytic activity
methoxy protons exhibit three distinct resonances with a than that with 5 and affords branched aldehydes exclusively
1:2:2 ratio. The 13C NMR resonances of the bridging meth- (Entries 5–8). Thus, the rhodium catalyst system combined
ylene carbon atoms appear at δ = 29.84, 30.33, and with 3 or 5 displays a high catalytic activity for the hydro-
30.54 ppm in a ratio of 1:1:1. All these NMR spectroscopic formylation of various terminal alkenes.
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Monophosphanylcalix[6]arene Ligands
FULL PAPER
Agriculture at Hokkaido University. Elemental analysis was per-
formed at the Center for Instrumental Analysis of Hokkaido Uni-
versity. Molecular-orbital calculations were performed with the
Gaussian 03 program[41] on a HIT HPC-IA642/SS 1.3/3D-4G.
5,11,17,23,29,35-Hexa-tert-butyl-37-(diphenylphosphanylmethoxy)-
38,39,40,41,42-pentamethoxycalix[6]arene (2): Ph2P(O)CH2OTs[14]
(0.44 g, 1.1 mmol) was added to a suspension of 1[13] (1.04 g,
1.0 mmol) and NaH (24 mg, 10 mmol) in 24 mL of toluene. The
reaction mixture was heated to 90 °C and stirred at this tempera-
ture for 2 d. After cooling, the unreacted NaH was neutralized
carefully by adding aq. 3% HCl. The crude product was extracted
with chloroform and dried with MgSO4. Analytically pure product
was obtained by medium-pressure column chromatography with
ethyl acetate as an eluent, followed by recrystallization from dichlo-
romethane/ethanol (1:5). Yield: 1.20 g (95 %). M.p. 172–174 °C.
(3)
Table 4. RhI-catalyzed hydroformylations of terminal olefins.[a]
Entry
Olefin
Ligand
Aldehydes [%]
Linear/branched[b]
1
2
3
4
5
6
7
8
1-hexene
3
5
3
5
3
5
3
5
79
85
81
91
67
24
96
57
66:34
71:29
8:92
styrene
10:90
[c]
vinyl acetate
vinyl benzoate
–
[c]
–
[c]
1
ESI-MS: m/z = 1256 [M]+. H NMR (CDCl3): δ = 0.83 (s, 9 H),
–
[c]
–
0.98 (s, 18 H), 1.26 (s, 9 H), 1.29 (s, 18 H), 2.23 (s, 6 H, OCH3),
2
2.70 (s, 3 H, OCH3), 3.32 (d, JH,H = 15 Hz, 2 H, ArCH2Ar), 3.37
[a] Olefin (1.0 mmol), [Rh(COD)2]BF4 (0.005 mmol), ligand (3 or
5) (0.02 mmol) in benzene (2 mL) at 70 °C under 10 atm CO/H2
(1:1). [b] Determined by GC. [c] No linear adduct was detected.
2
(s, 6 H, OCH3), 3.62 (d, JH,H = 14 Hz, 2 H, ArCH2Ar), 3.76 (d,
2
2JH,H = 14 Hz, 2 H, ArCH2Ar), 4.12 (d, JH,H = 14 Hz, 2 H, Ar-
2
2
CH2Ar), 4.16 (d, JH,H = 15 Hz, 2 H, ArCH2Ar), 4.25 (d, JH,H
=
14 Hz, 2 H, ArCH2Ar), 4.74 [d, 2JP,H = 7 Hz, 2 H, OCH2P(O)Ph2],
6.68 (s, 2 H), 6.77 (s, 2 H), 6.86 (s, 2 H), 7.13 (s, 2 H), 7.15 (s, 4
H), 7.45–7.58 (m, 6 H), 8.03–8.10 (m, 4 H) ppm. 13C{1H} NMR
(CDCl3): δ = 29.90, 30.14, 30.19, 31.05, 31.25, 31.48, 31.52, 33.97,
34.00, 34.13, 59.73, 59.86, 60.00, 71.20 [d, JP,C = 96 Hz,
OCH2P(O)Ph2], 124.23, 124.47, 124.87, 126.78, 127.15, 127.43,
In conclusion, novel monophosphanylcalix[6]arene li-
gands having mono-O-diphenylphosphanylmethyl (3) and
mono-O-(4-diphenylphosphanylphenyl)methyl (5) moieties
have been prepared, and complexation of 3 with PtII and
RhI complexes has been carried out. Conformational analy-
1
2
1
sis of the ligands and complexes suggests that the cone is 128.70 (d, JP,C = 11 Hz), 130.84 (d, JP,C = 110 Hz), 131.70 (d,
2JP,C = 9 Hz), 132.30, 132.86, 133.20, 133.24, 133.52, 133.58,
the most stable conformer in both solution and the solid
state. However, in the crystalline state, due to a small energy
difference between the cone and 1,2,3-alternate conforma-
tions, facile interconversion between these conformations
takes place to afford the 1,2,3-alternate conformation by
preferential crystallization of this conformer.
3
145.60, 145.64, 146.56, 151.95 (d, JP,C = 13 Hz), 153.34, 154.14,
1 5 4 . 3 2 p p m . 3 1 P { 1 H } N M R ( C D C l 3 ) : δ = 2 7 . 9 p p m .
C84H105O7P·H2O (1275.7): calcd. C 79.08, H 8.45; found C 79.44,
H 8.40.
5,11,17,23,29,35-Hexa-tert-butyl-37-(diphenylphosphanylmethoxy)-
38,39,40,41,42-pentamethoxycalix[6]arene (3): PhSiH3 (2.78 g,
25.8 mmol) was added to a solution of 2 (1.08 g, 0.86 mmol) in
20 mL of toluene. The reaction mixture was refluxed for 2 d and
then cooled down. After evaporation of the volatiles, an analyti-
Experimental Section
General: All reactions were performed under argon using standard
Schlenk techniques. Solvents were dried and purified before use by
usual methods.[38] [Rh(COD)2]BF4,[39] [PtCl2(COD)],[40] and
cally pure product was obtained by recrystallization from dichloro-
methane/ethanol (1:5). Yield: 0.96 g (90%). M.p. 117–119 °C. ESI-
1
MS: m/z = 1264 [M + Na]+. H NMR (CDCl3): δ = 0.92 (s, 9 H),
5,11,17,23,29,35-hexa-tert-butyl-38,39,40,41,42-pentamethoxycalix- 1.06 (s, 18 H), 1.27 (s, 9 H), 1.30 (s, 18 H), 2.50 (s, 6 H, OCH3),
2
[6]aren-37-ol (1)[15] were prepared according to literature pro-
cedures. Medium-pressure column chromatography (Yamazen
YFLC-540) was performed on silica gel (Wakogel C-400HG; par-
ticle size 20–40 µm) with a UV detector (Yamazen UV-10V). Pre-
parative-scale GPC was carried out with a Japan Analytical Indus-
try LC-9104 instrument equipped with Jaigel-1H-40 and Jaigel-2H-
40. 1H (400 MHz), 13C{1H} (100 MHz), and 31P{1H} NMR
(162 MHz) spectra were recorded with a Bruker ARX 400 instru-
ment. The 1H NMR spectroscopic data are referenced relative to
residual protonated solvent (δ = 5.32 and 7.26 ppm in CD2Cl2 and
CDCl3, respectively). 13C NMR chemical shifts are reported rela-
tive to either CD2Cl2 (δ = 53.1 ppm) or CDCl3 (δ = 77.0 ppm). The
31P NMR spectroscopic data are given relative to external 85%
H3PO4. HMBC[20] 2D NMR spectra were recorded with a JEOL α-
500 or a JEOL ECX-400 instrument. CPMAS solid-state 13C{1H}
NMR (100 MHz) spectra were recorded with a JEOL CMXP400
or a JEOL ECX-400 instrument with magic-angle spinning at
8 kHz (for 3) or 5 kHz (for 5); the 13C NMR spectroscopic data
are referenced relative to hexamethylbenzene (δ = 17.4 ppm). FD
and ESI mass spectra were recorded with a JEOL JMS-SX102A
instrument at the GC-MS & NMR Laboratory of the Faculty of
2.81 (s, 3 H, OCH3), 3.26 (s, 6 H, OCH3), 3.48 (d, JH,H = 15 Hz,
2
2 H, ArCH2Ar), 3.70 (d, JH,H = 14 Hz, 2 H, ArCH2Ar), 3.85 (d,
2JH,H = 15 Hz, 2 H, ArCH2Ar), 4.03 (d, JH,H = 15 Hz, 2 H, Ar-
2
2
2
CH2Ar), 4.19 (d, JH,H = 14 Hz, 2 H, ArCH2Ar), 4.35 (d, JH,H
=
2
15 Hz, 2 H, ArCH2Ar), 4.74 (d, JP,H = 4 Hz, 2 H, OCH2PPh2),
6.78 (s, 2 H), 6.87 (s, 2 H), 6.93 (s, 2 H), 7.11 (s, 2 H), 7.15 (s, 2
H), 7.24 (s, 2 H), 7.34–7.38 (m, 6 H), 7.60–7.63 (m, 4 H) ppm.
13C{1H} NMR (CDCl3): δ = 30.38, 30.48, 30.64, 31.15, 31.30,
31.49, 31.53, 33.99, 34.04, 34.15, 59.88, 59.92, 60.00, 74.74 (d, 1JP,C
= 9 Hz, OCH2PPh2), 124.20, 124.82, 125.11, 126.62, 126.78,
2
127.42, 128.50 (d, JP,C = 6.3 Hz), 128.83, 133.18, 133.30, 133.42,
133.45, 133.62, 136.37 (d, 1JP,C = 11 Hz), 145.57, 145.90, 153.25 (d,
3JP,C = 5 Hz), 153.56, 154.20, 154.38 ppm. 13C{1H} NMR (CDCl3):
δ = 30.38, 30.48, 30.64, 31.15, 31.30, 31.49, 31.53, 33.99, 34.04,
1
34.15, 59.88, 59.92, 60.00, 74.74 (d, JP, C = 9 Hz, OCH2PPh2),
124.20, 124.82, 125.11, 126.62, 126.78, 127.42, 128.50 (d, JP,C
2
=
6.3 Hz), 128.83, 133.18, 133.30, 133.42, 133.45, 133.62, 136.37 (d,
1JP,C = 11.4 Hz), 145.57, 145.90, 153.25 (d, JP,C = 5 Hz), 153.56,
3
154.20, 154.38 ppm. 13C{1H} NMR (CD2Cl2): δ = 30.44, 30.53,
30.81, 31.38, 31.48, 31.63, 31.68, 34.34, 34.43, 60.20, 60.24, 60.37,
75.02 (d, 1JP,C = 9 Hz, OCH2PPh2), 124.60, 125.09, 125.41, 127.19,
Eur. J. Inorg. Chem. 2006, 222–230
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
227

Y. Obora, Y. K. Liu, S. Kubouchi, M. Tokunaga, Y. Tsuji
FULL PAPER
127.40, 127.89, 128.90 (d, JP,C = 6 Hz), 129.30, 133.57, 133.69,
133.88, 133.99, 136.83 (d, 1JP,C = 11 Hz), 146.06, 146.37, 153.50 (d,
2
was then concentrated to about 0.5 mL under vacuum and the
product was precipitated with ethanol (3 mL). The solid obtained
3JP,C = 5 Hz), 153.85, 154.54, 154.70 ppm. 31P{1H} NMR (CDCl3): was filtered and washed with ethanol to afford a pure product.
1
δ = –16.5 ppm. C84H105O6P·CH2Cl2 (1326.6): calcd. C 76.95, H Yield: 172 mg (78%). ESI-MS: m/z = 2770 [M + Na]+. H NMR
8.13; found C 76.91, H 8.14.
(CDCl3): δ = 0.76 (s, 18 H), 0.88 (s, 36 H), 1.31 (s, 18 H), 1.32 (s,
36 H), 2.03 (s, 12 H, OCH3), 2.43 (s, 6 H, OCH3), 3.05 (d, 2JH,H
15 Hz, 4 H, ArCH2Ar), 3.47–3.57 (m, 16 H, OCH3 overlapped with
=
5,11,17,23,29,35-Hexa-tert-butyl-37-{(4-diphenylphosphanylphenyl)-
methoxy}-38,39,40,41,42-pentamethoxycalix[6]arene (4): Ph2P(O)
C6H4CH2Br[15] (0.782 g, 1.17 mmol) was added to a suspension of
1 (1.00 g, 0.95 mmol) and NaH (46 mg, 1.90 mmol) in DMF
(25 mL). The reaction mixture was heated to 50 °C and stirred for
20 h. After cooling to room temperature, the unreacted NaH was
slowly quenched with MeOH and H2O. The crude product was
extracted with Et2O/toluene (3:1) and dried with MgSO4. After fil-
tration, the solvent was removed in vacuo and analytically pure
product was obtained as a light-yellow solid by preparative GPC
using chloroform as an eluent. Yield: 1.19 g (94%). FD-MS: m/z =
1334 [M]+. 1H NMR (CDCl3): δ = 0.97 (s, 9 H), 1.01 (s, 18 H),
1.23 (s, 27 H), 2.50 (s, 6 H, OCH3), 2.76 (s, 3 H, OCH3), 3.21 (s, 6
2
2
ArCH2Ar), 3.66 (d, JH,H = 15 Hz, 4 H, ArCH2Ar), 3.72 (d, JH,H
2
= 15 Hz, 4 H, ArCH2Ar), 4.23 (d, JH,H = 15 Hz, 4 H, ArCH2Ar),
2
4.30 (d, JH,H = 15 Hz, 4 H, ArCH2Ar), 5.07 (br. s, 4 H,
OCH2PPh2), 6.51 (br. s, 4 H), 6.69 (br. s, 4 H), 6.74 (br. s, 4 H),
7.06 (br. s, 4 H), 7.10–7.23 (m, 16 H), 7.27–7.37 (m, 4 H), 7.78–
7.90 (m, 8 H) ppm. 13C{1H} NMR (CDCl3): δ = 29.84, 30.33,
30.54, 31.40, 31.60, 31.98, 34.33, 34.38, 34.57, 59.82, 60.34, 77.27,
77.59, 124.24, 124.63, 125.40, 126.53, 127.49, 127.66, 128.22,
128.76, 131.90, 133.14, 133.44, 133.55, 133.93, 134.05, 135.06,
135.15, 136.37 145.87, 146.01, 146.91, 153.47, 154.70 ppm. 31P{1H}
N M R ( C D C l 3 ) : δ = 6 . 0 ( 1 J P t , P = 3 6 1 1 H z ) p p m .
C168H210Cl2O12P2Pt·CH2Cl2 (2834.3): calcd. C 71.62, H 7.54;
found C 71.45, H 7.57.
2
2
H, OCH3), 3.51 (d, JH,H = 15 Hz, 2 H, ArCH2Ar), 3.66 (d, JH,H
2
= 15 Hz, 2 H, ArCH2Ar), 3.79 (d, JH,H = 15 Hz, 2 H, ArCH2Ar),
2
2
4.05 (d, JH,H = 15 Hz, 2 H, ArCH2Ar), 4.16 (d, JH,H = 15 Hz, 2
[Rh(COD)(3)2]BF4: A solution of ligand 3 (100 mg, 0.08 mmol) in
CH2Cl2 (12 mL) was added to a solution of [Rh(COD)2]BF4
(17.2 mg, 0.04 mmol) in 6 mL of THF over a period of 15 min. The
2
H, ArCH2Ar), 4.41 (d, JH,H = 15 Hz, 2 H, ArCH2Ar), 4.90 (s, 2
4
4
H), 6.82 (d, JH,H = 2 Hz, 2 H), 6.88 (s, 2 H), 6.89 (d, JH,H
=
2 Hz, 2 H), 7.08 (d, 4JH,H = 3 Hz, 2 H), 7.11 (s, 2 H), 7.19 (d, 4JH,H solution was stirred at room temperature for 3 h. Removal of the
= 3 Hz, 2 H), 7.44–7.72 (m, 14 H) ppm. 13C{1H}NMR (CDCl3): δ solvent gave a crude product as yellow solid, which was purified by
= 30.38, 30.79, 31.36, 31.43, 31.62, 31.70, 34.18, 34.22, 34.26, 59.95,
reprecipitation from CH2Cl2 solution with hexane. Yield: 72.4 mg
– +
1
60.06, 60.11, 73.55, 124.84, 125.06, 125.31, 126.83, 127.07, 127.27, (68%). ESI-MS: m/z = 2694 [M – BF4 ] . H NMR (CDCl3): δ =
127.37 (d, 2JP,C = 12 Hz), 128.63 (d, 2JP,C = 12 Hz), 131.27, 132.03, 0.76 (s, 18 H), 0.91 (s, 36 H), 1.30 (s, 18 H), 1.34 (s, 36 H), 2.09 (s,
132.22 (d, 3JP,C = 10 Hz), 132.45 (d, 3JP,C = 11 Hz), 133.11, 133.33, 12 H, OCH3), 2.24–2.41 (m, 8 H), 2.46 (s, 6 H, OCH3), 2.58 (br.,
133.52, 133.63, 133.69, 133.89, 142.17, 142.19, 145.76, 145.87, 4 H), 2.66 (d, J = 15 Hz, 4 H, ArCH2Ar), 3.51 (s, 12 H, OCH3),
2
146.34, 151.78, 153.68, 154.30, 154.38 ppm. 31P{1H}NMR
(CDCl3): δ = 29.6 ppm. C90H109O7P·CHCl3 (1453.2): calcd. C
75.21, H 7.63; found C 75.12, H 7.77.
3.61 (d, J = 14 Hz, 4 H, ArCH2Ar), 3.66 (d, JH,H = 15 Hz, 4 H,
2
2
ArCH2Ar), 4.23 (d, JH,H = 15 Hz, 4 H, ArCH2Ar), 4.30 (d, JH,H
= 15 Hz, 4 H, ArCH2Ar), 4.54 (br., 4 H, OCH2PPh2), 5.10 (br., 4
H), 6.46 (br., 4 H), 6.72 (br., 4 H), 6.78 (br., 4 H), 6.99 (br., 4 H),
7.16 (br., 4 H), 7.19 (br., 4 H), 7.34–7.47 (m, 12 H), 7.86–7.98 (m,
8 H) ppm. 13C{1H} NMR (CDCl3): δ = 30.04, 30.27, 30.45, 31.16,
31.42, 31.62, 31.96, 32.00, 34.32, 34.40, 34.61, 60.01, 60.39, 77.62,
99.10, 124.40, 124.84, 127.60, 127.92, 128.56, 129.60, 132.02,
132.78, 132.92, 133.53, 133.88, 133.97, 134.93, 146.09, 146.78,
152.45, 153.47, 154.60 ppm. 31P{1H} NMR (CDCl3): δ = 20.8 (d,
1JRh,P = 141 Hz) ppm. C176H222BF4O12P2Rh·CH2Cl2 (2866.2):
calcd. C 74.17, H 7.88; found C 74.27, H 7.91.
5,11,17,23,29,35-Hexa-tert-butyl-37-{(4-diphenylphosphanylphenyl)-
methoxy}-38,39,40,41,42-pentamethoxycalix[6]arene (5): A suspen-
sion of 4 (800 mg, 0.60 mmol) in toluene (12 mL) was refluxed in
the presence of PhSiH3 (2.2 mL, 18.0 mmol) for 2 d. The solvent
was then removed under reduced pressure and the residue dissolved
in CH2Cl2 (2 mL). Reprecipitation with MeOH afforded the prod-
uct as a white solid. Analytically pure product was obtained by
recrystallization from dichloromethane/MeOH (2:5). Yield: 646 mg
1
(82%). FD-MS: m/z = 1318 [M]+. H NMR (CDCl3): δ = 0.97 (s,
9 H), 1.02 (s, 18 H), 1.23 (s, 9 H), 1.24 (s, 18 H), 2.49 (s, 6 H,
Hydroformylation: In a typical experiment, [Rh(COD)2]BF4 (2 mg,
0.005 mmol) and 3 (25 mg, 0.02 mmol) were introduced into a 50-
mL stainless-steel autoclave (Toyo koatsu) under argon. Benzene
(2 mL), decane (71 mg, 0.5 mmol, as an internal standard), and 1-
2
OCH3), 2.76 (s, 3 H, OCH3), 3.22 (s, 6 H, OCH3), 3.51 (d, JH,H
2
= 15 Hz, 2 H, ArCH2Ar), 3.68 (d, JH,H = 15 Hz, 2 H, ArCH2Ar),
2
2
3.81 (d, JH,H = 15 Hz, 2 H, ArCH2Ar), 4.04 (d, JH,H = 15 Hz, 2
2
H, ArCH2Ar), 4.16 (d, JH,H = 15 Hz, 2 H, ArCH2Ar), 4.43 (d, hexene (84 mg, 1 mmol) were then added and the resulting solution
2JH,H = 15 Hz, 2 H, ArCH2Ar), 4.86 (s, 2 H, CH2), 6.82 (d, JH,H was stirred under argon for 1 h. The autoclave was then pressurized
4
2
= 2 Hz, 2 H), 6.87 (s, 2 H), 6.90 (d, JH,H = 2 Hz, 2 H), 7.08 (d,
to 10 atm with H2/CO (1:1) and the reaction mixture was stirred at
2JH,H = 2 Hz, 2 H), 7.11 (s, 2 H), 7.22 (d, 2JH,H = 2 Hz, 2 H), 7.30– 70 °C for 16 h. The products were analyzed by GC and GC-MS
7.34 (m, 12 H), 7.49–7.52 (m, 2 H) ppm. 13C NMR (CDCl3): δ = and the structures were confirmed by spectral comparison with au-
30.42, 30.76, 30.80, 31.32, 31.39, 31.59, 34.15, 34.16, 34.24, 59.91,
thentic aldehydes. The GC yields were determined by the internal
60.01, 60.09, 73.94, 124.66, 125.02, 125.23, 126.86, 127.01, 127.38, standard method.
2
2
127.81 (d, JP,C = 8 Hz), 128.59 (d, JP,C = 7 Hz), 128.78, 130.19,
133.32, 133.44, 133.67, 133.72, 133.90, 133.93, 134.13, 145.71,
145.79, 146.10, 151.95, 153.64, 154.30, 154.39 ppm. 31P NMR
(CDCl3): δ = –5.62 ppm. C90H109O6P·CH3OH (1349.8): calcd. C
80.97, H 8.44; found C 80.63, H 8.32.
X-ray Crystallography: Details of the crystal data and a summary
of intensity data collection parameters for 3 and [PtCl2(3)2] are
given in Table 5. Single crystals of 3 and [PtCl2(3)2] were grown by
slow diffusion of ethanol into a toluene solution of 3 and diffusion
of methanol into a toluene solution of [PtCl2(3)2]. Data were col-
lected with a Rigaku Saturn CCD diffractometer area detector with
graphite-monochromated Mo-Kα radiation (λ = 0.7107 Å) to a
maximum 2θ value of 55.0°. The structures were solved by direct
methods using the program SIR2002[42] and expanded using Fou-
[PtCl2(3)2]: A solution of ligand 3 (200 mg, 0.16 mmol) in CH2Cl2
(10 mL) was added to a solution of [PtCl2(COD)] (29.9 mg,
0.08 mmol) in 6 mL of CH2Cl2 over a period of 15 min. The solu-
tion was stirred at room temperature for 2 h. The resulting solution
228
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 222–230

Monophosphanylcalix[6]arene Ligands
FULL PAPER
Table 5. Crystal and structure refinement data for 3 and [PtCl2(3)2].
Param
3
[PtCl2(3)2]
Empirical formula
Formula mass
Temperature [°C]
Wavelength [Å]
Crystal system
Space group
C84H105O6P·C7H8·0.5C2H6O
C168H210Cl2O12P2Pt·4C7H8
1356.90
–160(1)
0.71070
triclinic
3182.09
–160(1)
0.71070
triclinic
¯
¯
P1(#2)
P1(#2)
a [Å]
b [Å]
c [Å]
α [°]
11.557(2)
12.946(6)
28.47(3)
81.4(1)
79.01(12)
84.89(10)
4126.7(46)
2
21.50(7)
24.63(10)
18.83(7)
100.61(8)
106.98(5)
97.96(7)
9174.8(60)
2
β [°]
γ [°]
V [Å3]
Z
Dcalcd. [gcm–3]
1.092
0.85
1.152
8.66
µ [cm–1]
Crystal size [mm]
No. of reflections measured
No. of unique reflections, Rint
R1
wR2
0.30×0.10×0.06
33429
0.30×0.20×0.16
90674
16706, 0.045
90564, 0.085
[a]
0.099[b]
0.098[c]
0.107[d]
0.223[e]
GOF
1.145
1.164
2
2
[a] R1 = Σ||Fo| – |Fc||/Σ|Fo|. [b] I Ͼ 2.3σ(I). [c] I Ͼ 2.0σ(I). [d] wR2 [I Ͼ 2.3σ(I)] = [Σw(|Fo| – |Fc|)2/ΣwFo
]
2 1/2, w = [0.0010Fo + 3.0000σ(Fo
)
+ 0.5000]–1. [e] wR2 (all data) = [Σ{w(Fo –Fc ) }/Σw(Fo2)2]1/2, w = [σ2(Fo2) + (0.0713P)2 + 43.3300P]–1 where P = [Max(Fo2,0) + 2Fc ]/3.
2
2 2
2
rier techniques.[43] For 3, non-hydrogen atoms except some of the
Phosphine Complexes (Ed.: L. H. Pignolet), Plenum, New
York, 1983.
solvent molecules were refined anisotropically. Hydrogen atoms
were included in fixed positions. The final cycle of full-matrix least-
squares refinement on F was based on 8953 observed reflections [I
Ͼ 2.3σ(I)] and 881 variable parameters. A Sheldrick weighting
scheme was used. For [PtCl2(3)2], non-hydrogen atoms except some
tert-butyl carbon atoms and solvent molecules were refined aniso-
tropically. Some tert-butyl carbon atoms were disordered over mul-
tiple positions, which were refined isotropically at fixed positions
with appropriate occupation factors without hydrogen atoms. Hy-
drogen atoms were refined using the riding model. The final cycle
of full-matrix least-squares refinement on F2 was based on 41459
observed reflections (using all data) and 1785 variable parameters.
Neutral-atom scattering factors were taken from Cromer and
Waber.[44] Anomalous dispersion effects were included in Fc.[45] All
calculations were performed with the CrystalStructure[46] crystallo-
graphic software package except for the refinement of [PtCl2(3)2],
which was performed with SHELXH-97.[47] CCDC-278415 (3)
and -278416 [PtCl2(3)2] contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.
ac.uk/data_request/cif.
[4]
We have recently prepared a bowl-shaped phosphane and a
phosphane-containing dendrimer unit, see: a) O. Niyomura, M.
Tokunaga, Y. Obora, T. Iwasawa, Y. Tsuji, Angew. Chem. Int.
Ed. 2003, 42, 1287; b) B. S. Balaji, Y. Obora, D. Ohara, S. Ko-
ide, Y. Tsuji, Organometallics 2001, 20, 5342.
[5]
For selected recent examples of phosphanylcalix[4]arenes, see:
a) S. Kim, J. S. Kim, O. J. Shon, S. S. Lee, K. M. Park, S. O.
Kang, J. Ko, Inorg. Chem. 2004, 43, 2906; b) P. Kuhn, C. Jeu-
nesse, D. Sémeril, D. Matt, P. Lutz, R. Welter, Eur. J. Inorg.
Chem. 2004, 4602; c) F. Plourde, K. Gilbert, J. Gagnon, P. D.
Harvey, Organometallics 2003, 22, 2862; d) M. Lejeune, C. Jeu-
nesse, D. Matt, N. Kyritsakas, R. Welter, J. P. Kintzinger, J.
Chem. Soc., Dalton Trans. 2002, 1642; e) C. Kunze, D. Selent, I.
Neda, R. Schmutzler, A. Spannenberg, A. Börner, Heteroatom
Chem. 2001, 12, 577; f) C. Dieleman, S. Steyer, C. Jeunesse, D.
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