Preparation, properties, and reactions of metal-containing heterocycles: Part CVI. Three-dimensional water-soluble platinacyclophanes

Article abstract of DOI:10.1016/S0022-328X(01)00866-X

Trifunctional primary phosphines of the type 1,3,5-[PH₂(CH₂)_n]₃C₆H₃ (3b-d) were obtained via an Arbusov reaction between the 1,3,5-tris(bromoalkyl)benzenes 1b-d and P(OEt)₃ follo

Full text of DOI:10.1016/S0022-328X(01)00866-X

Journal of Organometallic Chemistry 630 (2001) 244–252
www.elsevier.com/locate/jorganchem
Preparation, properties, and reactions of metal-containing
heterocyclesꢀ
Part CVI. Three-dimensional water-soluble platinacyclophanes
Ekkehard Lindner *, Monther Khanfar
Institut fu¨r Anorganische Chemie, Uni6ersita¨t Tu¨bingen, Auf der Morgenstelle 18, D-72076 Tu¨bingen, Germany
Received 14 March 2001; received in revised form 24 April 2001; accepted 29 April 2001
Dedicated to Professor Hans-Georg von Schnering on the occasion of his 70th birthday.
Abstract
Trifunctional primary phosphines of the type 1,3,5-[PH2(CH2)n]3C6H3 (3b–d) were obtained via an Arbusov reaction between
the 1,3,5-tris(bromoalkyl)benzenes 1b–d and P(OEt)3 followed by reaction of the trisphosphonates 1,3,5-
a
[(EtO)2P(O)(CH2)n]3C6H3 (2b–d) with LiAlH4. A straightforward conversion of these sensitive key phosphines 3b–d to the
corresponding water-soluble ligands 1,3,5-tris[bis(hydroxymethyl)phosphinylalkyl]benzenes 4b–d and 1,3,5-tris[bis(2%-diethylphos-
phonatoethyl)phophinylalkyl]benzenes 5b–d was achieved by formylation with formaldehyde and hydrophosphonation with
diethyl vinylphosphonate, respectively. A five component self-assembly consisting of three equivalents of the platinum(II) complex
Cl2Pt(NCPh)2 and two equivalents of the ligands 5b–d under high dilution conditions resulted in the formation of the nanoscaled,
water-soluble triplatinacyclophanes 6b–d in high yields. However, comparable reactions with the ligands 4b–d led only to
polymeric materials, which are insoluble in all organic solvents and water. The structures of the metallacyclophanes 6b–d were
elucidated by 31P{1H}-, 13C{1H}-, and 195Pt{1H}-NMR spectroscopic investigations. © 2001 Elsevier Science B.V. All rights
reserved.
Keywords: Metallacyclophanes; Platinum; P ligands; Supramolecular chemistry; Water-soluble complexes
processes necessary to sustain all functions of life.
Therefore, complexation studies in aqueous media are
of special interest since they can directly model molecu-
lar recognition in biologic systems [3,7]. Cyclophanes
are capable to form stable inclusion complexes with
apolar organic molecules in water, because they possess
accessible lipophilic cavities. It has been shown that
apolar complexation is stronger in aqueous solutions
compared to organic solvents [3,15,16]. This fact is due
to interactions between the lipophilic cavity and the
guest molecules [8].
Recently, it was demonstrated that 1,3,5-tris-
(diphenylphosphinylalkyl)benzenes are able to undergo
self-assembly with a suitable platinum complex to give
three-dimensional metallacyclophanes [9,10]. The incor-
poration of a metal fragment into cyclophanes leads to
a new type of macromolecules, with the ability to alter,
enhance, or create new properties for these systems [11].
1. Introduction
Supramolecular chemistry has been rapidly expand-
ing at the frontiers of chemical science with physical
and biological phenomena [2–7,13,14]. An important
application in this field is constituted by molecular
recognition. Cyclophanes belong to a special class in
supramolecular chemistry and usually they are provided
with cages suitable for the inclusion of guest molecules
[5–7]. Host–guest interactions are established to mimic
enzymes in their capability to bind substrates fast,
selectively and reversibly and to catalyze chemical reac-
tions [3,6,7]. Water is an essential biological fluid,
which promotes apolar aggregation and complexation
ꢀ For Part CV, see Ref. [1].
* Corresponding author. Tel.: +49-7071-297-2039; fax: +49-
7071-295-306.
E-mail address: ekkehard.lindner@uni-tuebingen.de (E. Lindner).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)00866-X

E. Lindner, M. Khanfar / Journal of Organometallic Chemistry 630 (2001) 244–252
245
spacer units carrying a phosphine substituent each at
their ends. These phosphines are provided with hydroxy
or phosphonate functions and are able to self-assemble
with platinum precursor complexes. The inclusion be-
havior in water toward several guests was tested.
By introduction of suitable functional groups it should
be possible to develop also water-soluble metallacy-
clophanes. Diederich et al. reported on the host–guest
chemistry of a specific cyclophane, which displays solu-
bility in solvents of all polarities [3,12,17]. To the best
of our knowledge similar studies have not yet been
carried out with metallacyclophanes. To achieve this
goal, novel tridentate water-soluble phosphine ligands
were generated. They are based on a central benzene
ring, which is provided with three flexible aliphatic
2. Results and discussion
2.1. Ligand synthesis
A straightforward Arbosuv reaction between the cor-
responding 1,3,5-tris(bromoalkyl)benzenes 1a–d and
triethyl phosphite afforded the 1,3,5-tris[(diethoxy-
phosphinyl)alkyl]benzenes 2a–d (Scheme 1). Reduction
by LiAlH4 in diethyl ether results in the formation of
the respective triprimary phosphines 3a–d (Scheme 1).
With the exception of 3a, which decomposed readily to
the 3,5-bis(phosphinylmethyl)toluene and PH3, 3b–d
were obtained in pure form. A similar decomposition
was also observed in the case of tris(hydroxy-
methyl)phosphine [18]. Several efforts were made to
prevent decomposition by employing lower temperature
and/or milder reducing agents (e.g. NaBH4), but they
were unsuccessful and led to unreacted material or
decomposition products. The phosphorus compounds
2a–d and 3b–d represent hygroscopic viscous oils and
colorless liquids, respectively, which are very sensitive
to air, in particular in the case of 3b–d. Therefore,
3b–d were not further purified after extraction from the
reaction mixture and they were directly used for the
next step. The composition of 2a–d and 3b–d was
corroborated by EI mass spectra showing the molecular
peak in each case. As expected in the 31P{1H}-NMR
spectra of 2a–d (in CDCl3) a singlet each is observed
(l=27.1–33.5) which is markedly shifted to higher
field (l: −136) by the reduction of 2b–d to 3b–d.
The trisphosphines 3b–d are regarded as key syn-
thons for the synthesis of the water-soluble phosphine
ligands 4b–d and 5b–d (Scheme 2), because they can
easily be converted to the related products by addition
or substitution reactions with regard to the PꢀH func-
tions [19]. Two examples were examined: (1) formyla-
tion of 3b–d by an aqueous solution of formaldehyde
in ethanol [18,20,21]; and (2) hydrophosphination of
diethyl vinylphosphonate with 3b–d [22–25] (Scheme
2). Both reactions proceeded quantitatively to afford
4b–d and 5b–d as viscous oils resistant to crystalliza-
tion. These novel phosphine ligands show good solubil-
ity in water, however, 4c and d need about 10% of
additional methanol to be soluble. Furthermore 5b–d
are soluble in solvents of medium polarity. The compo-
sitions of 4b–d and 5b–d were corroborated by FD and
FAB mass spectra showing the expected molecular
Scheme 1. Synthesis of the triprimary phosphines 3b–d.
1
peak in each case. H-, 13C{1H}-, and 31P{1H}-NMR
Scheme 2. Ligands synthesis.
spectra are consistent with the given structures (see

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E. Lindner, M. Khanfar / Journal of Organometallic Chemistry 630 (2001) 244–252
Scheme 3. Water-soluble cage-structured triplatinacyclophanes.
Scheme 2 and Section 4). It is characteristic for the
31P{1H}-NMR spectra of 5b–d that they display two
signals in a 2:1 ratio representing an A2X spin system
with a coupling constant of about 50 Hz. It is assigned
to the phosphonate (l=32) and phosphine (l: −20)
groups.
in the range of 3500–2500 Hz, respectively [27–30]. In
the spectra of 6b–d occur two signals with a 2:1 ratio
representing an A2XX%A% pattern. The A-part (pseudo-
2
triplet) of this spin system is located at higher field
(l:30, m, N=58 Hz [31a]) and ascribed to the phos-
phonate function, whereas the X-part (pseudo-pentet)
at lower field (l=5–13, m, N=58 Hz [31b]) which is
flanked by satellites at 91/2 (1JPtP) arising from scalar
coupling to the 33% abundant 195Pt nuclei [59] is at-
tributed to the phosphine groups. This assignment is
confirmed by 195Pt{1H}-NMR spectra, which display a
triplet each at l : −3940 ppm with coupling con-
stants of about 1JPtP=2450 Hz. The size of these
constants unequivocally points to a trans-PꢀPtꢀP ar-
rangement in the macrocycles 6b–d, which is in con-
trast to the recently reported nonwater-soluble
platinacyclophanes [9,10]. The different stereochemistry
can be traced back to the greater steric demand of the
phosphonate substituents at the phosphorus atoms
compared to phenyl groups [32–37].
2.2. Self-assembly of the ligands 5b–d with
Cl2Pt(NCPh)2
To obtain self-assembled cyclophane structures, a
preorganization of the components is a necessary pre-
requisite. The trifunctionalized phosphines 4b–d and
5b–d are provided with specific substituents that make
them water-soluble. In addition they have the indis-
pensable rigidity, which is required to be preorganized.
For the generation of the three-dimensional water-solu-
ble platinacyclophanes 6b–d, the ligands 5b–d were
treated with Cl2Pt(NCPh)2 in a mixture of methanol
and dichloromethane or only dichloromethane, respec-
tively, according to the high dilution method [26]
(Scheme 3). Corresponding reactions with 4b–d as
starting materials led only to colorless polymers, which
were not further characterized. The self-assembled
triplatinacyclophanes 6b–d could be obtained in much
higher yields (40–70%) than their nonwater-soluble
counterparts [9,10]. The yields decreased by increasing
the number of methylene groups in the sequence 6b\
6c\6d.
The pale yellow triplatinacyclophanes 6b–d are solu-
ble in water and organic solvents of medium polarity.
Several experiments to grow single crystals of 6b–d for
an X-ray structural analysis failed.
An insight into structural facts of the platinacy-
clophanes 6b–d is available by 31P{1H}-NMR spectro-
scopic probes. 31P chemical shifts and 195Pt–31P
coupling constants allow an unambiguous distinction
between cis and trans arrangement of the ligands at the
platinum center. Corresponding coupling constants are
1
As the line patterns in the H- and 13C{1H}-NMR
spectra of the methylene groups could not be resolved,
1
a short discussion of the H- and 13C{1H}-NMR spec-
tra of the triplatinacyclophanes 6b–d refers to the
1
central benzene rings. Only one H signal is observed at
l:6.8 which is an indication of the C3 symmetry of
these molecules. In the aromatic region of 13C{1H}-
NMR spectra, two resonances correspond to the me-
thine (l:126) and quaternary (l:141) carbon atoms.
NMR spectroscopy is considered as the method of
choice to study inclusion complexation in solution [3].
Extensive information is obtained on the structures of
the complexes. Furthermore, the thermodynamics and
kinetics of complexation can be evaluated. The metalla-
cyclophanes 6b–d have the advantage to be soluble in
many solvents of different polarity and the 31P nucleus
serves as a probe for NMR titrations. Several neutral
organic guest (e.g. halogenated hydrocarbons, benzoic
acid, potassium p-fluorobenzenesulfonate, fluorinated

E. Lindner, M. Khanfar / Journal of Organometallic Chemistry 630 (2001) 244–252
247
4. Experimental
benzenes, toluene, 1,3,5-triacetylbenzene, and 1,3,5-
trimesic acid) of different size were tested for the encap-
sulation into the cavities of 6b–d employing water or
10–30% (v/v) aqueous methanol as solvents. The
amount of 6b–d covered the accessible concentration
range. However, no significant change of the chemical
shifts for the 31P or 1H signals resulting from the
phosphine and aromatic moiety, respectively, could be
observed.
4.1. General
All synthetic reactions and manipulations were per-
formed under dry argon atmosphere using standard
Schlenk techniques. Dichloromethane was freshly dis-
tilled from calcium hydride, and diethyl ether from
sodium benzophenone ketyl. Column chromatography:
activated silica gel, 0.063–0.200 mm or 0.04–0.063
(Merck); column dimensions are reported in the specific
sections describing the synthesis of the compounds.
Purifications by thin layer chromatography were car-
ried out on preparative TLC glass plates (20×20 cm)
using silica gel 60 F254, 0.5 mm (Merck). Elemental
analysis, Elementar Vario EL analyzer. Mass spectra,
EI-MS, Finnigan TSQ 70 eV (200 °C); FD and FAB-
MS, Finnigan 711A (8 kV), modified by AMD. IR,
Bruker IFS 48 FT-IR. 1H-, 13C{1H}-, 31P{1H}-, and
195Pt{1H}-NMR, Bruker DRX-250 spectrometer oper-
ating at 250.13, 62.90, 101.26, and 53.55 MHz, respec-
3. Conclusions
Within the last 5–10 years, several new architectures
of metallacyclophanes with interesting properties have
been described in the literature [38–47]. This new vari-
ant of cyclophanes is available by the self-assembly of
multifunctional ligands with suitable metal fragments.
Recently, several metallacyclophanes were introduced
which were formed by a template synthesis in aqueous
media [48–51]. The solvent effect in self-assembly is
also reported in the literature [52]. In the present inves-
tigation, a simple strategy is presented that allows a
convenient access to novel water-soluble trifunctional
phosphines. They are provided with a central benzene
ring, which has three phosphine arms in a symmetrical
1, 3 and 5 position. The distance of these phosphines
from the benzene ring is controlled by methylene func-
tions of different length. To these phosphines water-sol-
uble functional groups are attached. It was
demonstrated that these water-soluble trifunctional
phosphine ligands are capable to undergo self-assembly
with adequate platinum complex fragments to form
triplatinacyclophanes. The tendency of self-organiza-
tion is reduced by increasing the number of methylene
groups. In that case the ligand system becomes more
flexible and the phosphine moieties are able to move
away from each other to minimize the interactions and
hence the steric demand. Concomitant the production
of polymers is enhanced.
The triplatinacyclophanes 6b–d are soluble in sol-
vents of different polarity and even in water. Because of
this favorable property they should be able to include
guest molecules. However, experiments in this direction
failed and did not lead to reproducible or significant
changes of the chemical shifts of 1H or 31P signals in the
corresponding NMR spectra of these compounds [3].
This drawback may be attributed to three effects: (i)
external p–p stacking interactions leading to self-asso-
ciation of the hosts [3]; (ii) the host–guest association
constants are too small to be measured; (iii) ethyl
groups (24) at the phosphorus atoms may block the
entrance of the cavities and hence prevent the encapsu-
lation of guest molecules.
1
tively. H-NMR chemical shifts were referred to TMS
as internal standard. 13C{1H}-NMR chemical shifts
were calibrated against the deuterated solvent multiplet
and referenced to TMS. 31P{1H}-NMR chemical shifts
were measured relative to external 85% H3PO4 with
downfield values being taken as positive. 195Pt{1H}-
NMR chemical shifts were measured relative to exter-
nal 37.5% Na2[PtCl6] · 6 H2O. Triethylphosphite and
2,2%-azobis(2-methylpropionitrile) (AIBN) were ob-
tained from commercial suppliers and used without
further purification. Compounds 1a [53], 1b [54], 1c [9],
1d [55], diethyl vinylphosphonic ester [56], and
Cl2Pt(NCPh)2 [57] were synthesized according to litera-
ture methods.
4.2. Preparation of 1,3,5-tris[(diethoxyphosphinyl)-
alkyl]benzenes 2a–d [58]
A mixture of 1a–d (10 mmol) and triethylphosphite
(20 ml, 117 mmol) was heated in a two-necked 50 ml
round-bottomed flask equipped with a distillation con-
denser. The temperature was maintained at 145–
150 °C. After the distillation of ethylbromide is
finished, the reaction mixture was further heated for 2 h
at the same temperature. Excess triethylphosphite was
removed in vacuo to leave the pure products 2a–d.
4.2.1. 1,3,5-Tris[(diethoxyphosphinyl)methyl]benzene
(2a)
This compound was first reported in the literature by
several authors [60] but 2a was not properly character-
ized. Colorless oil (5.0 g, 95%). FAB-MS (NBA,
50 °C); m/z (%): 551 (4) [M+Na]+, 529 (100) [M+
H]+, 392 (21) [M−P(O)(OEt)2]+. MS (FD, CH2Cl2,
30 °C); m/z: 528 [M]+, 1057 [2M+H]+. IR (KBr,

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E. Lindner, M. Khanfar / Journal of Organometallic Chemistry 630 (2001) 244–252
cm−1): w˜ =2982, 2908 (CH2), 1603 (aromat. CꢁC), 1252
(PꢁO), 1028 (PꢀOEt). 31P{1H}-NMR (101.26 MHz,
CDCl3, 22 °C): l=27.1. 1H-NMR (250.13 MHz,
CDCl3, 22 °C): l=1.10 (t, 3JHH=7.1 Hz, 18H,
(O)(OEt)2]+. Anal. Found: C, 55.24; H, 8.50. Calc. for
C30H57O9P3 (654.7): C, 55.04; H, 8.78%. IR (KBr,
cm−1): w˜ =2981, 2938, 2865 (CH2), 1603 (aromat.
CꢁC), 1245 (PꢁO), 1060 (PꢀOEt). 31P{1H}-NMR
(101.26 MHz, CDCl3, 22 °C): l=33.5. 1H-NMR
(250.13 MHz, CDCl3, 22 °C): l=1.31 (t, 3JHH=7.1
Hz, 18H, OCH2CH3), 1.72–1.80 (m, 18H, CH2CH2-
CH2CH2P), 2.55 (t, 3JHH=7.2 Hz, 6H, CH2CH2
CH2CH2P), 4.08 (dq, 3JHH=6.8 Hz, 3JPH=6.8 Hz,
2
OCH2CH3), 2.96 (d, JPH=22.0 Hz, 6H, CH2P), 3.87
(dq, 3JHH=7.4 Hz, 3JPH=7.4 Hz, 12H, OCH2CH3),
4
6.99 (d, JPH=2.2 Hz, 3H, aromat. C6H3). 13C{1H}-
3
NMR (62.90 MHz, CDCl3, 22 °C): l=16.3 (d, JPC
=
1
5.7 Hz, CH3CH2O), 33.3 (d, JPC=138.0 Hz, CH2P),
2
3
61.9 (d, JPC=7.1 Hz, CH3CH2O), 129.7 (dt, JPC
=
=
12H, OCH2CH3), 6.78 (s, 3H, aromat. CH). 13C{1H}-
5
2
3
11.0 Hz, JPC=5.7 Hz, aromat. CH), 132.1 (td, JPC
NMR (62.90 MHz, CDCl3, 22 °C): l=16.7 (d, JPC
=
4
2
12.1, JPC=3.6 Hz, aromat. C).
5.7 Hz, CH3CH2O), 22.5 (d, JPC=5.0 Hz, CH2CH2P),
25.7 (d, JPC=140.9 Hz, CH2P), 32.7 (d, JPC=17.1
Hz, CH2CH2CH2P), 35.6 (s, CH2CH2CH2CH2P), 61.6
1
3
4.2.2. 1,3,5-Tris[2%-(diethoxyphosphinyl)ethyl]benzene
(2b)
2
(d, JPC=6.4 Hz, CH3CH2O), 126.1 (s, aromat. CH),
Colorless oil (5.6 g, 98%). FAB-MS (NBA, 50 °C);
m/z: 571 [M+H]+. Anal. Found: C, 50.86; H, 8.03.
Calc. for C24H45O9P3 (570.5): C, 50.52; H, 7.95%. IR
(KBr, cm−1): w˜ =2983, 2870 (CH2), 1605 (aromat.
CꢁC), 1234 (PꢁO), 1024 (PꢀOEt). 31P{1H}-NMR
(101.26 MHz, CDCl3, 22 °C): l=31.8. 1H-NMR
(250.13 MHz, CDCl3, 22 °C): l=1.25 (t, 3JHH=7.1
142.2 (s, aromat. C).
4.3. Preparation of the
1,3,5-tris(phosphinoalkyl)benzenes 3b–d [24]
A diethyl ether (100 ml) solution of 2b–d (3 mmol) in
a pressure-equalizing dropping funnel was added slowly
within 3 h to a stirred suspension of powdered LiAlH4
(0.96 g, 27 mmol) in diethyl ether (150 ml) at −10 °C
(ice–salt bath). The reaction mixture was allowed to
warm slowly to room temperature (r.t.). After stirring
for 48 h at r.t., the reaction was hydrolyzed slowly with
aqueous hydrochloric acid (6M, 50 ml) at −10 °C
(ice–salt bath). The ether layer was separated and the
aqueous phase was extracted with diethyl ether (2×100
ml). The combined ether extracts were dried (Na2SO4)
and removed under reduced pressure to give a clear
residual liquid, which was identified as pure 3b–d.
2
3
Hz, 18H, OCH2CH3), 1.94 (td, JPH=17.3 Hz, JHH
=
3
3
7.1 Hz, 6H, CH2P), 2.78 (dt, JPH=9.3 Hz, JHH=7.1
Hz, 6H, CH2CH2P), 4.03 (dq, 3JHH=7.2 Hz, 3JPH=7.2
Hz, 12H, OCH2CH3), 6.82 (s, 3H, aromat. CH).
13C{1H}-NMR (62.90 MHz, CDCl3, 22 °C): l=16.5
3
1
(d, JPC=6.4 Hz, CH3CH2O), 27.6 (d, JPC=139.4 Hz,
CH2P), 28.5 (d, 2JPC=5.0 Hz, CH2CH2P), 61.9 (d,
2JPC=6.4 Hz, CH3CH2O), 125.8 (s, aromat. CH), 141.7
3
(d, JPC=17.8 Hz, aromat. C).
4.2.3. 1,3,5-Tris[3%-(diethoxyphosphinyl)propyl]benzene
(2c)
Colorless oil (6.0 g, 98%). MS (70 eV, EI, 200 °C);
m/z (%): 612 (7) [M]+, 475 (9) [M−P(O)(OEt)2]+, 461
(41) [M−CH2P(O)(OEt)2]+. Anal. Found: C, 52.64; H,
8.19. Calc. for C27H51O9P3 (612.6): C, 52.94; H, 8.39%.
IR (KBr, cm−1): w˜ =2981, 2938, 2865 (CH2), 1602
(aromat. CꢁC), 1245 (PꢁO), 1042 (PꢀOEt). 31P{1H}-
NMR (101.26 MHz, CDCl3, 22 °C): l=33.2. 1H-NMR
(250.13 MHz, CDCl3, 22 °C): l=1.22 (t, 3JHH=7.1
Hz, 18H, OCH2CH3), 1.61 (m, 6H, CH2CH2P), 1.85 (m,
4.3.1. 1,3,5-Tris(2%-phosphinoethyl)benzene (3b)
Colorless liquid (0.50 g, 64%). MS (70 eV, EI,
200 °C); m/z (%): 258 (1) [M]+, 225 (100) [M−PH2]+.
IR (KBr, cm−1): w˜ =2969, 2923 (CH2), 2290 (PꢀH),
1603 (aromat. CꢁC). 31P{1H}-NMR (101.26 MHz,
1
CDCl3, 22 °C): l= −136.8. H-NMR (250.13 MHz,
CDCl3, 22 °C): l=1.72 (m, 6H, CH2P), 2.62 (td,
1JPH=195.3 Hz, 3JHH=7.5 Hz, 6H, PH2), 2.71 (dt,
3
3JPH=7.9 Hz, JHH=7.5 Hz, 6H, CH2CH2P), 6.76 (s,
3
6H, CH2P), 2.54 (t, JHH=7.2 Hz, 6H, CH2CH2CH2P),
3H, aromat. CH). 13C{1H}-NMR (62.90 MHz, CDCl3,
22 °C): l=16.1 (d, 1JPC=9.2 Hz, CH2P), 39.2 (d,
2JPC=2.9 Hz, CH2CH2P), 126.3 (s, aromat. CH), 142.4
3.99 (dq, 3JHH=7.4 Hz, 3JPH=7.3 Hz, 12H,
OCH2CH3), 6.73 (s, 3H, aromat. CH). 13C{1H}-NMR
3
3
(62.90 MHz, CDCl3, 22 °C): l=16.4 (d, JPC=5.7 Hz,
(d, JPC=5.0 Hz, aromat. C).
CH3CH2O), 24.2 (d, 2JPC=5.0 Hz, CH2CH2P), 25.2 (d,
1JPC=140.9 Hz, CH2P), 36.4 (d, 3JPC=17.1 Hz,
CH2CH2CH2P), 61.4 (d, 2JPC=6.4 Hz, CH3CH2O),
126.4 (s, aromat. CH), 141.3 (s, aromat. C).
4.3.2. 1,3,5-Tris(3%-phosphinopropyl)benzene (3c)
Colorless liquid (0.6 g, 67%). MS (70 eV, EI, 200 °C);
m/z (%): 300 (1) [M]+, 267 (100) [M−PH2]+. IR (KBr,
cm−1): =2964, 2874 (CH2), 2292 (PꢀH), 1603 (aromat.
CꢁC). 31P{1H}-NMR (101.26 MHz, CDCl3, 22 °C):
4.2.4. 1,3,5-Tris[4%-(diethoxyphosphinyl)butyl]benzene
(2d)
1
l= −136.1. H-NMR (250.13 MHz, CDCl3, 22 °C):
Colorless oil (6.5 g, 99%). MS (70 eV, EI, 200 °C);
l=1.53 (dt, 3JHH=7.9 Hz, 2JPH=6.9 Hz, 6H,
CH2P), 1.82 (dtt, 3JPH=8.1 Hz, 3JHH=6.9 Hz,
m/z (%): 654 (18) [M]+, 489 (100) [M−CH2CH2P-

E. Lindner, M. Khanfar / Journal of Organometallic Chemistry 630 (2001) 244–252
249
3
3JHH=7.5 Hz, 6H, CH2CH2P), 2.62 (t, JHH=7.5 Hz,
CH2P), 31.8 (d, 2JPC=17.1 Hz, CH2CH2P), 59.3 (d,
1JPC=15.7, PCH2O), 125.3 (s, aromat. CH), 142.7 (d,
3JPC=12.8 Hz, aromat. C).
1
3
6H, CH2CH2CH2P), 2.71 (dt, JPH=194.7 Hz, JHH
=
7.2 Hz, 6H, PH2), 6.80 (s, 3H, aromat. CH). 13C{1H}-
NMR (62.90 MHz, CDCl3, 22 °C): l=13.5 (d,
1JPC=8.5 Hz, CH2P), 34.8 (d, 2JPC=2.9 Hz,
CH2CH2P), 36.7 (d, 3JPC=5.7 Hz, CH2CH2CH2P),
126.2 (s, aromat. CH), 141.7 (s, aromat. C).
4.4.2. 1,3,5-Tris[3%-bis(hydroxymethyl)phosphinopropyl]-
benzene (4c)
Clear gummy material (0.90 g, 94%). FAB-MS
(NBA, 50 °C); m/z (%): 481 (20) [M+H]+, 449 (28)
[M−CH2OH]+, 420 (33) [M−2CH2O]+. Anal.
Found: C, 52.31; H, 8.50. Calc. for C21H39O6P3 (480.5):
C, 52.50; H, 8.18%. IR (KBr, cm−1): w˜ =3346 (OꢀH),
2899 (CH2), 1600 (aromat. CꢁC), 1012 (CꢀO). 31P{1H}-
NMR (101.26 MHz, D2O, 22 °C): l= −24.5. 31P{1H}-
NMR (101.26 MHz, acetone-d6, 22 °C): l= −22.9.
1H-NMR (250.13 MHz, D2O, 22 °C): l=1.86 (dd,
2JPH=7.2 Hz, 3JHH=7.2 Hz, 6H, CH2P), 2.76 (dt,
4.3.3. 1,3,5-Tris(4%-phosphinobutyl)benzene (3d)
Colorless liquid (0.7 g, 68%). MS (70 eV, EI,
200 °C); m/z (%): 341 (1) [M−H]+, 309 (100) [M−
PH2]+. IR (KBr, cm−1): w˜ =2963, 2925, 2853 (CH2),
2290 (PꢀH), 1602 (aromat. CꢁC). 31P{1H}-NMR
1
(101.26 MHz, CDCl3, 22 °C): l= −136.0. H-NMR
(250.13 MHz, CDCl3, 22 °C): l=1.55 (m, 12H,
CH2CH3CH2P), 1.67 (m, 6H, CH2CH2P), 2.56 (t,
3JHH=7.4 Hz, 6H, CH2CH2CH2CH2P), 2.69 (dt,
3
3JPH=9.5 Hz, JHH=7.6 Hz, 6H, CH2CH2P), 3.98 (m,
1JPH=194.7 Hz, JHH=6.9 Hz, 6H, PH2), 6.80 (s, 3H,
12H, OCH2P), 7.02 (s, 3H, aromat. CH). 1H-NMR
(250.13 MHz, acetone-d6, 22 °C): l=2.06 (m, 6H,
CH2P), 2.82 (m, 6H, CH2CH2P), 4.13 (m, 12H,
OCH2P), 7.07 (s, 3H, aromat. CH). 13C{1H}-NMR
3
aromat. CH). 13C{1H}-NMR (62.90 MHz, CDCl3,
22 °C): l=13.8 (d, 1JPC=7.4 Hz, CH2P), 32.6 (d,
2
3JPC=5.4 Hz, CH2CH2CH2P), 32.7 (d, JPC=2.7 Hz,
1
CH2CH2P), 35.6 (s, CH2CH2CH2CH2P), 126.1 (s, aro-
(62.90 MHz, D2O, 22 °C): l=20.0 (d, JPC=8.6 Hz,
mat. CH), 142.5 (s, aromat. C).
CH2P), 29.1 (d, 2JPC=15.3 Hz, CH2CH2P), 55.8 (d,
1JPC=9.53 Hz, PCH2O), 123.8 (s, aromat. CH), 140.7
(d, 3JPC=9.5 Hz, aromat. C). 13C{1H}-NMR (62.90
4.4. Preparation of the 1,3,5-tris[bis(hydroxymethyl)-
phosphinoalkyl]benzenes 4b–d
1
MHz, acetone-d6, 22 °C): l=20.2 (d, JPC=11.4 Hz,
CH2P), 31.8 (d, 2JPC=17.1 Hz, CH2CH2P), 59.3 (d,
To a vigorously stirred solution of compounds 3b–d
(2 mmol) in ethanol (20 ml) a degassed solution of
aqueous formaldehyde (37%, 1.0 g, 12 mmol) in ethanol
(5 ml) was added dropwise at r.t. The reaction mixture
was allowed to stir at r.t. for 12 h. Removal of volatile
materials in vacuo afforded the pure compounds 4b–d.
1JPC=15.7 Hz, PCH2O), 125.3 (s, aromat. CH), 142.7
3
(d, JPC=12.8 Hz, aromat. C).
4.4.3. 1,3,5-Tris[4%-bis(hydroxymethyl)phosphinobutyl]-
benzene (4d)
Clear gummy material (1.0 g, 96%). FAB-MS (NBA,
50 °C); m/z (%): 523 (20) [M+H]+, 491 (15) [M−
CH2OH]+, 462 (28) [M−2CH2O]+. Anal. Found: C,
54.97; H, 8.88. Calc. for C24H45O6P3 (522.5): C, 55.17;
H, 8.68%. IR (KBr, cm−1): =3346 (OꢀH), 2899 (CH2),
1600 (aromat. CꢁC), 1012 (CꢀO). 31P{1H}-NMR
4.4.1. 1,3,5-Tris[2%-bis(hydroxymethyl)-
phosphinoethyl]benzene (4b)
Clear gummy material (0.85 g, 97%). FAB-MS
(NBA, 50 °C); m/z (%): 439 (41) [M+H]+, 408 (42)
[M−CH2O]+, 378 (41) [M−2CH2O]+. Anal. Found:
C, 49.45; H, 7.76. Calc. for C18H33O6P3 (438.4): C,
49.32; H, 7.59%. IR (KBr, cm−1): w˜ =3346 (OꢀH),
2899 (CH2), 1600 (aromat. CꢁC), 1012 (CꢀO). 31P{1H}-
NMR (101.26 MHz, D2O, 22 °C): l= −24.5. 31P{1H}-
NMR (101.26 MHz, acetone-d6, 22 °C): l= −22.9.
1H-NMR (250.13 MHz, D2O, 22 °C): l=1.86 (dd,
2JPH=7.2 Hz, 3JHH=7.2 Hz, 6H, CH2P), 2.76 (dt,
1
(101.26 MHz, acetone-d6, 22 °C): l=ꢀ24.0. H-NMR
(250.13 MHz, acetone-d6, 22 °C): l=1.50–1.72 (m,
18H, CH2CH2CH2P), 2.58 (t, 3JHH=7.2 Hz, 6H,
CH2CH2CH2CH2P), 4.01 (m, 12H, OCH2P), 6.86 (s,
3H, aromat. CH). 13C{1H}-NMR (62.90 MHz, acetone-
1
d6, 22 °C): l=18.9 (d, JPC=10.1 Hz, CH2P), 26.5 (d,
2JPC=15.5 Hz, CH2CH2P), 34.1 (d, 3JPC=11.5 Hz,
CH2CH2CH2P), 36.2 (s, CH2CH2CH2CH2P), 60.6 (d,
3JPC=16.2 Hz, PCH2OH), 126.8 (s, aromat. CH), 143.2
(s, aromat. C).
3JPH=9.5 Hz, JHH=7.6 Hz, 6H, CH2CH2P), 3.98 (m,
3
12H, OCH2P), 7.02 (s, 3H, aromat. CH). 1H-NMR
(250.13 MHz, acetone-d6, 22 °C): l=2.06 (m, 6H,
CH2P), 2.82 (m, 6H, CH2CH2P), 4.13 (m, 12H,
OCH2P), 7.07 (s, 3H, aromat. CH). 13C{1H}-NMR
4.5. Preparation of the 1,3,5-tris{bis[(2%-diethylphos-
phonatoethyl)phosphinolkyl]}benzenes 5b–d
1
(62.90 MHz, D2O, 22 °C): l=20.0 (d, JPC=8.6 Hz,
CH2P), 29.1 (d, 2JPC=15.3 Hz, CH2CH2P), 55.8 (d,
1JPC=9.53 Hz, PCH2O), 123.8 (s, aromat. CH), 140.7
(d, 3JPC=9.5 Hz, aromat. C). 13C{1H}-NMR (62.90
A mixture of 3b–d (2.0 mmol), diethyl vinylphospho-
nate (2.17 g, 13.2 mmol), and AIBN (50 mg) was
irradiated with ultraviolet light of a mercury high pres-
sure lamp at 20 °C in a closed quartz Schlenk tube for
1
MHz, acetone-d6, 22 °C): l=20.2 (d, JPC=11.4 Hz,

250
E. Lindner, M. Khanfar / Journal of Organometallic Chemistry 630 (2001) 244–252
24 h. The volatile materials were removed under vac-
uum at 80 °C to leave the pure products 5b–d.
8.43%. IR (KBr, cm−1): w˜ =2983, 2933, 2857 (CH2),
1603 (aromat. CꢁC), 1240 (PꢁO), 1066 (PꢀOEt).
31P{1H}-NMR (101.26 MHz, CDCl3, 22 °C): l= −
3
3
4.5.1. 1,3,5-Tris{2%-bis[(2%-diethylphos-
phonatoethyl)phosphinoethyl]}benzene (5b)
21.1 (t, JPP=51.2 Hz, 3P, PC3), 32.4 (d, JPP=51.2
1
Hz, 6P, CP(O)(OEt)2). H-NMR (250.13 MHz, CDCl3,
Clear gummy material (2.4 g, 96%). MS (FD,
CH2Cl2, 35 °C); m/z: 1243 [M]+. Anal. Found: C,
46.24; H, 8.18. Calc. for C48H99O18P9 (1243.1): C,
46.38; H, 8.03%. IR (KBr, cm−1): w˜ =2983, 2908
(CH2), 1602 (aromat. CꢁC), 1237 (PꢁO), 1055 (PꢀOEt).
31P{1H}-NMR (101.26 MHz, CDCl3, 22 °C): l= −
22 °C): l=1.28 (t, 3JHH=7.1 Hz, 36H, OCH2CH3),
1.41 (br. s, 12H, CH2CH2P), 1.49–1.64 (m, 24H,
OꢁPCH2CH2P), 1.77 (m, 6H, CH2CH2CH2P), 2.50 (t,
3
3JHH=7.5 Hz, 6H, CH2CH2CH2P), 4.05 (dq, JHH
=
3
7.2 Hz, JPH=7.2 Hz, 24H, OCH2CH3), 6.74 (s, 3H,
aromat. CH). 13C{1H}-NMR (62.90 MHz, CDCl3,
22 °C): l=16.6 (d, 3JPC=6.1 Hz, CH3CH2O), 18.7
(dd, 1JPC=16.5 Hz, 2JPC=6.4 Hz, OꢁPCH2CH2P),
21.9 (dd, 1JPC=140.5 Hz, 2JPC=13.9 Hz,
3
3
19.6 (t, JPP=51.2 Hz, 3P, PC3), 32.2 (d, JPP=51.2
1
Hz, 6P, CP(O)(OEt)2). H-NMR (250.13 MHz, CDCl3,
22 °C): l=1.29 (t, 3JHH=7.1 Hz, 36H, OCH2CH3),
3
1.63–1.86 (m, 30H, CH2P(CH2CH2)2), 2.64 (dt, JPH
=
OꢁPCH2CH2P),
25.8
(d,
3JPC=10.8
Hz,
4.4 Hz, 3JHH=7.4 Hz, 6H, CH2CH2P), 4.07 (dq,
CH2CH2CH2P), 26.4 (d, JPC=13.5 Hz, CH2P), 33.5
1
3JHH=7.2 Hz, JPH=7.2 Hz, 24H, OCH2CH3), 6.82 (s,
(d,
CH2CH2CH2CH2P),
3JPC=13.5
Hz,
61.8
CH2CH2P),
35.8
(s,
3
3H, aromat. CH). 13C{1H}-NMR (62.90 MHz, CDCl3,
22 °C): l=16.2 (d, 3JPC=5.7 Hz, CH3CH2O), 18.3
(dd, 1JPC=17.4 Hz, 2JPC=6.8 Hz, OꢁPCH2CH2P),
21.5 (dd, 1JPC=140.5 Hz, 2JPC=13.9 Hz,
OꢁPCH2CH2P) 28.2 (d, 1JPC=15.7 Hz, CH2P), 31.6 (d,
(d,
2JPC=6.7
Hz,
CH3CH2O), 125.0 (s, aromat. CH), 142.4 (s, aromat.
C).
4.6. Preparation of the triplatinacyclophanes 6b–d
2JPC=14.9 Hz, CH2CH2P), 61.4 (d, 2JPC=6.4 Hz,
3
CH3CH2O), 125.4 (s, aromat. CH), 142.6 (d, JPC
=
Solutions of Cl2Pt(NCPh)2 (708 mg, 1.5 mmol) and
the corresponding ligand (1.0 mmol) in dichloro-
methane (250 ml) were simultaneously added dropwise
during 36 h into stirred dichloromethane (600 ml).
After the addition was complete, the reaction mixture
was allowed to stir for 24 h at r.t. Then the solvent was
removed in vacuo and the resulting residue was sub-
jected to column chromatography (30×3 cm, 15%
MeOH–CH2Cl2). TLC purifications were performed
for analysis.
11.4 Hz, aromat. C).
4.5.2. 1,3,5-Tris{3%-bis[(2%-diethylphos-
phonatoethyl)phosphinopropyl]}benzene (5c)
Clear gummy material (2.5 g, 97%). MS (FD,
CH2Cl2, 35 °C); m/z: 1285 [M]+. Anal. Found: C,
47.23; H, 7.97. Calc. for C51H105O18P9 (1285.1): C,
47.67; H, 8.23%. IR (KBr, cm−1): w˜ =2984, 2932, 2929
(CH2), 1603 (aromat. CꢁC), 1237 (PꢁO), 1026 (PꢀOEt).
31P{1H}-NMR (101.26 MHz, CDCl3, 22 °C): l= −
3
3
21.2 (t, JPP=51.2 Hz, 3P, PC3), 32.3 (d, JPP=51.2
4.6.1. 4,4,17,17,30,30-Hexachloro-3,3,5,5,16,16,18,
18,29,29,31,31-dodeca(2%-diethylphos-phonatoethyl)-
3,5,16,18,29,31-hexaphospha-4,17,30-triplatina[73]
(1,3,5)-cyclophane (6b)
1
Hz, 6P, CP(O)(OEt)2). H-NMR (250.13 MHz, CDCl3,
22 °C): l=1.22 (t, 3JHH=7.1 Hz, 36H, OCH2CH3),
1.35 (m, 6H, CH2P), 1.43–1.75 (m, 30H, OꢁPCH2CH2P
and CH2CH2P), 2.52 (t, 3JHH=7.4 Hz, 6H,
CH2CH2CH2P), 3.99 (dq, 3JHH=7.2 Hz, 3JPH=7.2 Hz,
Pale yellow gummy material (68 %). MS (pos. FAB,
NBA, 50 °C); m/z: 3288 [M]+, 3239 [M−OEt]+, 3202
[M−Cl−EtO]+. Anal. Found: C, 34.91; H, 6.05; Cl,
6.60. Calc. for C96H198Cl6O36P18Pt3 (3284.1): C, 35.11;
H, 6.08; Cl, 6.48%. IR (KBr, cm−1): w˜ =2981, 2930,
2910 (CH2), 1604 (aromat. CꢁC), 1239 (PꢁO), 1023
(PꢀOEt). 195Pt{1H}-NMR (CDCl3): l= −3940 (t,
1JPtP=2478 Hz). 31P{1H}-NMR (CD2Cl2): l=6.1 (m
24H, OCH2CH3), 6.70 (s, 3H, aromat. CH). 13C{1H}-
3
NMR (62.90 MHz, CDCl3, 22 °C): l=16.4 (d, JPC
=
5.7 Hz, CH3CH2O), 18.5 (dd, 1JPC=16.4 Hz,
2JPC=6.4 Hz, OꢁPCH2CH2P), 21.7 (dd, JPC=140.1
1
Hz, 2JPC=13.5 Hz, OꢁPCH2CH2P), 26.1 (d, JPC
=
2
1
14.2 Hz, CH2CH2P), 27.5 (d, JPC=14.2 Hz, CH2P),
37.3 (d, 3JPC=11.4 Hz, CH2CH2CH2P), 61.6 (d,
2JPC=6.4 Hz, CH3CH2O), 126.1 (s, aromat. CH),
141.8 (s, aromat. C).
1
[31b] d, N=58.1, JPtP=2478 Hz, 6P, PtPC3), 30.1 (m
31a, N=58.1 Hz, 12P, CP(O)(OEt)2). 1H-NMR (250.13
3
MHz, CD2Cl2, 22 °C): l=1.27 (t, JHH=7.1 Hz, 72H,
CH3), 1.52–2.28 (m, 60H, (OꢁPCH2CH2)2PCH2), 2.80
(br. s, 12H, CH2CH2P), 4.05 (m, 48H, OCH2), 6.82 (s,
3H, C6H3). 13C{1H}-NMR (62.90 MHz, CD2Cl2,
4.5.3. 1,3,5-Tris{4%-bis[(2%-diethylphospho-
natoethyl)phosphinobutyl]}benzene (5d)
Clear gummy material (2.55 g, 96%). FAB-MS
(NBA, 50 °C); m/z (%): 1327 (23) [M]+, 1161 (13)
[M−CH2CH2P(O)(OEt)2]+. Anal. Found: C, 48.70; H,
8.64. Calc. for C54H111O18P9 (1327.2): C, 48.87; H,
2
22 °C): l=13.1 (m, OꢁPCH2CH2P), 16.7 (d, JPC=5.7
Hz, CH3), 20.1 (d, 1JPC=140.1 Hz, OꢁPCH2CH2P),
27.3 (m, CH2P), 29.5 (br. s, CH2CH2P), 127.6 (s, aro-
mat. CH), 140.5 (s, aromat. C).

E. Lindner, M. Khanfar / Journal of Organometallic Chemistry 630 (2001) 244–252
251
4.6.2. 5,5,20,20,35,35-Hexachloro-4,4,6,6,19,19,21,21,
References
34,34,36,36-dodeca-(2%-diethylphos-phonatoethyl)-
4,6,19,21,34,36-hexaphospha-5,20,35-triplatina[93]-
(1,3,5)-cyclophane (6c)
[1] E. Lindner, U. Kehrer, M. Steimann, M. Stro¨bele, J.
Organomet. Chem. (2001), in press.
[2] J.-M. Lehn, Supramolecular Chemistry, VCH, Weinheim, 1995.
[3] F.N. Diederich, Cyclophanes, Royal Society of Chemistry, Cam-
bridge, 1991.
[4] F. Vo¨gtle, Cyclophan-Chemie, Teubner, Stuttgart, 1990.
[5] D.J. Cram, J.M. Cram, Container Molecules and their Guests,
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[6] B. Dietrich, P. Viout, J.-M. Lehn, Macrocyclic Chemistry: As-
pects of Organic and Inorganic Supramolecular Chemistry,
VCH, Weinheim, 1993.
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(b) C. Seel, F. Vo¨gtle, Angew. Chem. Int. Ed. Engl. 31 (1992)
528.
[8] S. Akine, K. Goto, R. Okazaki, Chem. Lett. (1999) 681.
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(2001), in press.
[10] E. Lindner, C. Hermann, G. Baum, D. Fenske, Eur. J. Inorg.
Chem. (1999) 679.
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Soc. 118 (1996) 6044.
[13] P. Ettmayer, A. Billich, P. Hecht, B. Rosenwirth, H. Gstach, J.
Med. Chem. 39 (1996) 3291.
Pale yellow gummy material (55%). MS (pos. FAB,
NBA, 50 °C); m/z: 3365 [M]+, 3233 [M−3EtO]+.
Anal. Found: C, 35.98; H, 6.06; Cl, 6.40. Calc. for
C102H210Cl6O36P18Pt3 (3368.2): C, 36.37; H, 6.28; Cl,
6.32%. IR (KBr, cm−1): w˜ =2981, 2930 (CH2), 1603
(aromat. CꢁC), 1242 (PꢁO), 1028 (PꢀOEt). 195Pt{1H}-
NMR (CDCl3): l= −3966 (t, 1JPtP=2465 Hz).
31P{1H}-NMR (101.26 MHz, CDCl3, 22 °C): l=15.2
1
(m [31b] d, N=58.2, JPtP=2465 Hz, 6P, PtPC3), 30.3
(m [31a], N=58.2 Hz, 12P, CP(O)(OEt)2). 1H-NMR
(250.13 MHz, CDCl3, 22 °C): l=1.33 (m, 72H, CH3),
1.74–2.06 (m, 72H, (OꢁPCH2CH2)2PCH2CH2), 2.59
(br. s, 12H, CH2CH2CH2P), 4.11 (m, 48H, OCH2), 6.76
(s, 3H, C6H3). 13C{1H}-NMR (62.90 MHz, CDCl3,
2
22 °C): l=12.1 (m, OꢁPCH2CH2P), 16.5 (d, JPC=5.4
Hz, CH3), 19.6 (d, 1JPC=141.5 Hz, OꢁPCH2CH2P),
24.4 (m, CH2CH2P), 35.1 (m, CH2P), 36.8 (s,
CH2CH2CH2P), 128.2 (s, aromat. CH), 141.0 (s, aro-
mat. C).
[14] G. Arena, A. Casnati, A. Contino, G.G. Lombardo, D. Sciotto,
R. Ungaro, Chem. Eur. J. 5 (1999) 738.
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[17] F. Diederich, K. Dick, D. Griebel, J. Am. Chem. Soc. 108 (1986)
2273.
4.6.3. 6,6,29,29,40,40-Hexachloro-5,5,7,7,22,22,24,
24,39,39,41,41-dodec(2%-diethylphos-phonatoethyl)-
5,7,22,24,39,41-hexaphospha-6,23,40-triplatina[113]-
(1,3,5)-cyclophane (6d)
Pale yellow gummy material (37%). MS (pos. FAB,
NBA, 50 °C); m/z: 3450 [M]+, 3417 [M−Cl]+. Anal.
Found: C, 37.65; H, 6.54, 6.38. Calc. for
[18] J.W. Ellis, K.N. Harrison, P.A.T. Hoye, A.G. Orpen, P.G.
Pringle, M.B. Smith, Inorg. Chem. 31 (1992) 3026.
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forsch. B 45 (1990) 203.
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32 (1999) 9.
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house, J.S. Parry, J. Chem. Soc. Dalton Trans. (1994) 977.
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Trans. 1 (1994) 977.
[26] P. Knops, N. Sendhoff, H.-B. Mekelburger, F. Vo¨gtle, High
dilution reactions – new synthetic applications, in: E. Weber, F.
Vo¨gtle (Eds.), Macrocycles. In: Topics in Current Chemistry,
vol. 161, Springer, Heidelberg, 1992.
[27] W.E. Hill, J.G. Taylor, C.P. Falshaw, T.J. King, B. Beagley,
D.M. Tonge, R.G. Pritchard, C.A. McAuliffe, J. Chem. Soc.
Dalton Trans. (1986) 2289.
[28] W. Hill, D.M.A. Minahan, J.G. Taylor, C.A. McAufliffe, J. Am.
Chem. Soc. 104 (1982) 6011.
C
108H222Cl6O36P18Pt3 (3452.4): C, 37.57; H, 6.48; Cl,
6.16%. IR (KBr, cm−1): w˜ =2981, 2930, 2860 (CH2),
1603 (aromat. CꢁC), 1242 (PꢁO), 1046 (PꢀOEt).
195Pt{1H}-NMR (CDCl3): l= −3933 (t, 1JPtP=2460
Hz). 31P{1H}-NMR (101.26 MHz, CDCl3, 22 °C): l=
1
12.9 (m [31b] d, N=58.2, JPtP=2460 Hz, 6P, PtPC3),
30.5 (m [31a], N=58.2 Hz, 12P, CP(O)(OEt)2). 1H-
NMR (250.13 MHz, CDCl3, 22 °C): l=1.34 (m, 72H,
CH3),
1.59–2.23
(m,
72H,
(OꢁPCH2CH2)2-
PCH2CH2CH2), 2.61 (br. s, 12H, CH2CH2CH2CH2P),
4.11 (m, 48H, OCH2), 6.76 (s, 3H, C6H3). 13C{1H}-
NMR (62.90 MHz, CDCl3, 22 °C): l=13.8 (m,
2
OꢁPCH2CH2P), 16.5 (d, JPC=6.1 Hz, CH3), 18.9 (s,
CH2CH2CH2P),
19.6
(d,
1JPC=141.5
Hz,
OꢁPCH2CH2P), 22.8 (s, CH2CH2CH2P), 32.4 (m,
CH2CH2P), 34.6 (s, CH2CH2CH2CH2P), 126.3 (s, aro-
mat. CH), 141.1 (s, aromat. C).
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[31] (a) A, Part of an A2XX%A%2 system N=ꢀ JPP+5JPPꢀ;
3
(b) X, Part of an A2XX%A2% system N=ꢀ JPP+5JPPꢀ: R.K. Har-
Support of this research by the Deutsche Forschungs-
gemeinschaft and the Fonds der Chemischen Industrie
is gratefully acknowledged. Degussa AG is thanked for
supplying platinum complexes as starting materials.
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