Preparation, properties, and reactions of metal-containing heterocycles: Part CV. Synthesis and structure of polyoxadiphosphaplatinaferrocenophanes

Article abstract of DOI:10.1016/S0022-328X(01)01006-3

A series of novel heterobimetallic crown ether-like polyoxadiphosphaplatinaferrocenophanes cis-[1,1′-Fc(CH₂O(CH₂CH₂O)_nCH₂CH₂PPh₂)₂]PtCl₂ (n=1-3) (4a-c) was synthesized in good yield by cyclization of the bis(phosphine) ligands 1,1′-Fc(CH₂O(CH₂CH₂O)_nCH₂CH₂PPh₂)₂ (n=1-3) (3a-c) and (PhCN)₂PtCl₂ under high dilution conditions in CH₂Cl₂. The bisphosphines 3a-c are obtained by reaction of the corresponding diols 1,1′-Fc(CH₂O(CH₂CH₂O)_nCH₂CH₂OH)₂ (n=1-3) (1a-c) with: (i) CH₃SO₂Cl in CH₂Cl₂ and (ii) LiPPh₂ in THF. Although the X-ray crystal structure of 4a shows that the cavity is large enough for the encapsulation of small metal cations, inclusion experiments of 4a-c with Group 1 cations, and Mg²⁺, or NH₄⁺ in solution applying NMR titration and cyclovoltammetric methods reveal no evidence for the formation of host-guest complexes for 4a,b. In the case of 4c only the addition of Na⁺ or K⁺ leads to an insignificant effect.

Full text of DOI:10.1016/S0022-328X(01)01006-3

Journal of Organometallic Chemistry 630 (2001) 266–274
www.elsevier.com/locate/jorganchem
Preparation, properties, and reactions of metal-containing
heterocyclesꢀ
Part CV. Synthesis and structure of
polyoxadiphosphaplatinaferrocenophanes
Ekkehard Lindner *, Ulf Kehrer, Manfred Steimann, Markus Stro¨bele
Institut fu¨r Anorganische Chemie der Uni6ersita¨t Tu¨bingen, Auf der Morgenstelle 18, D-72076 Tu¨bingen, Germany
Received 24 April 2001; accepted 9 May 2001
Abstract
A series of novel heterobimetallic crown ether-like polyoxadiphosphaplatinaferrocenophanes cis-[1,1%-Fc(CH2O(CH2CH2O)n-
CH2CH2PPh2)2]PtCl2 (n=1–3) (4a–c) was synthesized in good yield by cyclization of the bis(phosphine) ligands 1,1%-
Fc(CH2O(CH2CH2O)nCH2CH2PPh2)2 (n=1–3) (3a–c) and (PhCN)2PtCl2 under high dilution conditions in CH2Cl2. The
bisphosphines 3a–c are obtained by reaction of the corresponding diols 1,1%-Fc(CH2O(CH2CH2O)nCH2CH2OH)2 (n=1–3)
(1a–c) with: (i) CH3SO2Cl in CH2Cl2 and (ii) LiPPh2 in THF. Although the X-ray crystal structure of 4a shows that the cavity
is large enough for the encapsulation of small metal cations, inclusion experiments of 4a–c with Group 1 cations, and Mg2+, or
NH+4 in solution applying NMR titration and cyclovoltammetric methods reveal no evidence for the formation of host–guest
complexes for 4a,b. In the case of 4c only the addition of Na+ or K+ leads to an insignificant effect. © 2001 Elsevier Science B.V.
All rights reserved.
Keywords: Polyoxaplatinaferrocenophanes; Platinum complexes; Macrocyclization; High dilution
The objective of the present work was the incorpora-
tion of a potentially catalytically active metal center
and a redox active ferrocene unit into a crown ether-
like macrocycle. Such a combination is rarely described
in the literature [7,9,10]. The expected heterobimetallic
host molecules can be regarded as a crosslink between
polyoxa[n]ferrocenophanes [11] and metallacrown
ethers [12,13], which should be capable of including
different metal cations of the first or second main group
as guests. The ferrocene function offers the possibility
to electrochemically manipulate the inclusion
characteristics.
The hitherto successfully applied bis(triflate) method
for the formation of metal–carbon s bonds which is a
necessary precondition for the access to metallacy-
clophanes [5,14] and metallametallocenophanes [6]
failed when heteroatoms are incorporated into the
backbone of the bis(triflate) [12]. However, the well-de-
veloped phosphine chemistry offers a valuable alterna-
tive for the introduction of a second transition metal to
1. Introduction
Cyclophanes [2] and crown ethers [3] represent proto-
typic motifs in the development of supramolecular
chemistry. The introduction of transition metal frag-
ments into macrocyclic systems created a new and fast
growing field in supramolecular organometallic chem-
istry [4]. Compared to their organic analogues, metalla-
cyclophanes, metallocenophanes and metallacrown
ethers exhibit a variety of additional features, like cata-
lytic and/or redox activity [5–7]. Transition metals also
exert a remarkable influence on the structure of macro-
cycles with regard to their rigidity and cavity. It was
demonstrated that metal-containing macrocycles reveal
suitable hosts for the inclusion of guests, like metal ions
or small molecules [8].
ꢀ Part CIV, 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)01006-3

E. Lindner et al. / Journal of Organometallic Chemistry 630 (2001) 266–274
267
generate polyoxametallaferrocenophanes. Suitable bis-
(phosphine) ligands were built up of oligoethylene gly-
col chains with different length which are connected to
a ferrocene unit in 1,1%-positions and to two phospho-
rus donors. If these ligands are reacted with a transition
metal precursor in a 1:1 ratio under high dilution
conditions, the desired bimetallic crown ethers are
available.
erate yields as dark orange, hygroscopic, viscous oils.
Subsequently 1a–c were treated with excess methane-
sulfonyl chloride to give the dimesylates 2a–c which
were reacted with LiPPh2 in THF to afford the phos-
phines 3a–c. These ligands were obtained in good
yields as dark orange, slightly air-sensitive, viscous oils,
which are soluble in all common organic solvents. Their
molecular composition was corroborated by elemental
analyses and FD mass spectra displaying the expected
molecular peak in each case. In agreement with related
ligands [12], the 31P{1H}-NMR spectra of 3a–c display
singlets at l= −21 for both chemically equivalent
2. Results and discussion
1
phosphorus nuclei. The H- and 13C{1H}-NMR spectra
2.1. Synthesis of the bidentate phosphine ligands 3a–c
of the intermediates 1a–c and 2a–c and of 3a–c are
similar for the ferrocene moiety and oligoethylene gly-
col chains. Only the resonances of both methylene
groups at the open ends of the molecules show differ-
ences in the chemical shifts depending on the kind of
attached terminal functional group.
The bidentate phosphines 3a–c (Scheme 1) were
made accessible by coupling of in situ generated 1,1%-
bis(chloromethyl)ferrocene [15,16] to functionalized oli-
goethylene glycols. After purification by column
chromatography the diols 1a–c were obtained in mod-
2.2. Synthesis of the
polyoxadiphosphaplatinaferrocenophanes 4a–c
To enhance the formation of the heterobimetallic
macrocycles 4a–c (Scheme 1) and to suppress the oc-
currence of oligo- and/or polymeric species, the reac-
tion between the bisphosphines 3a–c and one
equivalent of bis(benzonitrile)dichloroplatinum(II) was
carried out under high dilution conditions in
dichloromethane [17]. After purification by column
chromatography the polyoxadiphosphaplatinaferro-
cenophanes 4a–c were obtained as bright yellow, rather
air stable solids, which readily dissolve in chlorinated
organic solvents and mixtures of them with any other
organic solvent. However, solutions of 4a–c slowly
decompose in the presence of air oxygen and traces of
an acid. In the FD mass spectra of 4a–c the molecular
peaks are detected with the appropriate isotopic pat-
terns. Compared to 3a–c the 31P signals in the 31P{1H}-
NMR spectra expectedly are shifted to lower field.
Resonances with superimposed doublets due to the
195Pt–31P coupling are observed at l=4.3 (4a) and
1
:5.3 (4b,c). The magnitude of the J(Pt,P) coupling
constant of approximately 3630 Hz gives evidence for
the cis-arrangement of the phoshpinyl functions in each
case [18]. This finding is confirmed by the 195Pt{1H}-
NMR spectra of 4a–c, displaying each a triplet at
l= −4400 with the same 1J(Pt,P) coupling. In the
high field part of the 13C{1H}-NMR spectra of 4a–c
the signals of the methylene groups adjacent to the P
atoms appear as the A part of an A%XX% spin system.
2.3. X-ray crystal structure of 4a
To prove the mononuclear composition of 4a–c and
to obtain more detailed information about the size and
Scheme 1. Synthesis of the bis(phosphine) ligands 3a–c and the
polyoxadiphosphaplatinaferrocenophanes 4a–c.

268
E. Lindner et al. / Journal of Organometallic Chemistry 630 (2001) 266–274
Fig. 1. Top: ORTEP plot of one molecule of the X-ray crystal structure of compound 4a. Thermal ellipsoids are drawn at 20% probability level,
except for H atoms. Bottom: space-filling representation of 4a.
Table 1
shape of the cavities, efforts to grow single crystals of
,
Selected interatomic distances (A) and interbond angles (°) for 4a
4a–c have been undertaken. Because of the flexibility of
the molecular skeleton of the platinaferrocenophanes,
only 4a could be crystallized. The triclinic unit cell
contains eight symmetrically independent molecules of
4a which differ only in minor conformational changes,
mainly in the oligoethylene glycol chains. An ORTEP
plot of one selected molecule with atom labeling is
depicted in Fig. 1 (top). Selected bond lengths and
angles are summarized in Table 1. All four oxygen
atoms are approximately located in a plane at the
vertices of a distorted trapezoid. The lengths of the
Interatomic distances
Pt(1)ꢀCl(1)
Pt(1)ꢀCl(2)
Pt(1)ꢀP(1)
Pt(1)ꢀP(2)
Pt(1)ꢀFe(1)
2.35(1) O(1)ꢀO(2)
2.36(1) O(1)ꢀO(3)
2.24(1) O(2)ꢀO(4)
2.26(1) O(3)ꢀO(4)
9.25(1)
2.83(3)
5.62(3)
4.74(3)
2.82(3)
Interbond angles
P(1)ꢀPt(1)ꢀP(2)
P(1)ꢀPt(1)ꢀCl(1)
P(2)ꢀPt(1)ꢀCl(2)
Cl(1)ꢀPt(1)ꢀCl(2)
98.8(2)
88.6(2)
86.5(2)
88.0(3)
C(1)ꢀP(1)ꢀPt(1)
114.8(10)
117.5(7)
114(3)
C(33)ꢀP(2)ꢀPt(1)
O(2)ꢀC(15)ꢀC(16)
O(4)ꢀC(5)ꢀC(6)
109(4)
,
parallel edges are 5.62(1) (O(1)ꢀO(3)) and 4.73(1) A

E. Lindner et al. / Journal of Organometallic Chemistry 630 (2001) 266–274
269
(O(2)ꢀO(4)) and the O(1)ꢀO(2) and O(3)ꢀO(4) distances
cations, resulting in shifts of the redox potential up to
300 mV have been reported [21]. However, no perturba-
tion of the cyclic voltammograms of 4a–c upon succes-
sive addition of Group 1 cations, Mg2+, or NH4 + ions
could be observed.
,
are 2.83(3) and 2.82(3) A, respectively. A distance of
,
9.25(1) A was found between Pt(1) and Fe(1). From
these proportions it can be deduced that the cavity is
large enough to encapsulate smaller alkaline or earth
alkaline metal ions. A space filling model (Fig. 1,
bottom) demonstrates this property. The coordination
sphere of platinum is not ideally square-planar, because
the ClꢀPtꢀCl plane is tilted against the PꢀPtꢀP plane by
14.7°. The coplanar cyclopentadienyl rings of the fer-
rocene unit are arranged in an almost eclipsed confor-
mation and the two substituents are displaced by one
ring carbon position.
3. Conclusion
With regard to the possibility of the electrochemically
controllable formation of host–guest complexes, a se-
ries of novel heterobimetallic crown ether-like poly-
oxadiphosphaplatinaferrocenophanes
4a–c
with
different ring size and number of oxygen donor atoms
was synthesized according to the high dilution method
and characterized. Inclusion experiments with alkaline
metal cations, and Mg2+, or NH+4 , respectively, were
2.4. In6estigations on the inclusion beha6ior and
electrochemical properties of the
polyoxadiphosphaplatinaferrocenophanes 4a–c
1
performed in solution applying H- and 31P{1H}-NMR
NMR titrations are among the most employed meth-
ods for the determination of association constants in
host/guest chemistry [19]. In addition to H-NMR, the
titrations and cyclic voltammetry. No evidence for the
formation of host–guest complexes was found for the
smaller cycles 4a,b, whereas in the case of 4c at least in
the 31P{1H}-NMR spectra a detectable shift was ob-
served upon addition of Na+ and K+. However, the
determination of the association constants by non-lin-
ear curve-fitting of the experimental data did not lead
to a satisfactory result. Although the X-ray crystal
structure of 4a shows that the cavity is large enough to
include guest ions of the mentioned type, the results of
the inclusion experiments revealed that no or only weak
complexation takes place. The steric demand of both
transition metal fragments is limiting the flexibility of
the macrocycles 4a–c to an extent that they are not
able to adopt an energetically favorable conformation
in which the oxygen donors can provide an approxi-
mately tetrahedral or octahedral environment which is
a necessary prerequisite for the complexation of the
metal cations under consideration.
1
polyoxadiphosphaplatinaferrocenophanes 4a–c offer
the possibility to use the 31P nucleus as a probe for
NMR titrations. Attempts to include alkaline metal
cations and Mg2+, or NH4 +, respectively, as potential
guests were performed in a mixture of CDCl3–CD3CN
(v/v 1:1) for several different starting concentrations of
4a–c, covering the accessible concentration range. In
the case of the smaller cycles 4a,b neither in the 1H- nor
in the 31P{1H}-NMR spectra a significant shift of any
signal could be observed. Only the addition of Na+ or
K+ to a solution of 4c resulted in a remarkable shift, in
particular of the 31P resonance up to Dl:1. However,
a satisfactory determination of association constants by
non-linear curve fitting of the experimental data with
EQNMR [20] was not possible. This observation can be
traced back to the insufficient fitting results for all
applied complexation models. Both 1:1 and 2:1 com-
plexes were taken into consideration, either separate or
parallel. Self-association has been ruled out by dilution
experiments. A possible explanation for this finding is
the fact that the association constants are too small.
Due to solubility limitations, the necessary concentra-
tions of the guests could not be achieved.
Cyclovoltammetric measurements of 4a–c were per-
formed in 5×10−4 M dichloromethane–acetonitrile
(v/v 1:1) solutions. The half-wave potentials for the
reversible oxidation of the ferrocene units in 4a–c are
152, 142, and 144 mV, respectively. These values corre-
spond to a slight anodic shift compared to the redox
potential of unsubstituted ferrocene (E°=136 mV),
measured in the same solvent mixture. Other cyclo-
voltammetric signals could not be detected within the
accessible potential range. Electrochemical response to
the formation of host–guest complexes of ferrocene-
containing crown ethers or cryptands, and metal
4. Experimental
4.1. General procedures
All manipulations were carried out under an atmo-
sphere of dry argon using standard Schlenk techniques.
Solvents, triethylamine, di-, tri-, and tetraethylene gly-
col (Merck) were dried with appropriate reagents, dis-
tilled and stored under argon. PCl3 was freshly distilled
under argon prior to use. Sodium hydride and
methanesulfonyl chloride were of commercial grade
(Fluka) and used without further purification; the latter
was stored under argon. Column chromatography was
performed using activated silica gel, 0.063–0.200 mm
(Merck). Column dimensions, eluent mixtures and spe-
cial conditions are reported in the specific sections
describing the synthesis of the compounds. Elemental

270
E. Lindner et al. / Journal of Organometallic Chemistry 630 (2001) 266–274
analyses were carried out with an Elementar Vario EL
analyzer. Cl analyses were carried out according to
Scho¨niger [22] and determined as described by
Dirscherl and Erne [23] according to Brunisholz and
Michot [24]. FD mass spectra were taken on a Finnigan
MAT 711 A instrument, modified by AMD. IR data
were obtained with a Bruker IFS 48 FT-IR spectrome-
ganic phases were dried with Na2SO4 and the solvent
was evaporated. The diols were separated from starting
material and monosubstituted by-product by column
chromatography (ethyl acetate–ethanol 5:1, diameter/
length of column 7/20 cm). The last fractions were
identified as the diols which were obtained as dark
orange hygroscopic viscous oils.
1
ter. H-, 31P{1H}-, 13C{1H}-, and 195Pt{1H}-NMR spec-
4.3. 1,1%-Bis(7-hydroxy-2,5-dioxaheptyl)ferrocene (1a)
tra were recorded at 25 °C on a Bruker DRX 250
spectrometer operating at 250.13, 101.25, 62.90, and
53.55 MHz, respectively. 1H and 13C chemical shifts
were measured relative to partially deuterated solvent
peaks and deuterated solvent peaks, respectively, which
are reported relative to TMS. 31P and 195Pt chemical
shifts were measured relative to external 85% H3PO4
and 37.5% Na2[PtCl6]6H2O, respectively. Cyclic voltam-
mograms were recorded with a Bioanalytical Systems
(BAS, West Lafayette, IN) CV-100 W electrochemical
workstation. A Metrohm Pt electrode tip (Filderstadt,
Germany) was used as working electrode, the counter
electrode was a Pt wire of 1 mm diameter. A single-unit
Haber–Luggin double reference-electrode [25] was
used. The resulting potential values refer to Ag/Ag+
(0.01 M in CH3CN–0.1 M NBu4PF6). A gas-tight
full-glass three-electrode cell was used, its assembly has
been described elsewhere [26]. The cell was purged with
argon before it was filled with the electrolyte. NBu4PF6
(0.1 M) was used as supporting electrolyte. Background
curves were recorded before adding the substrate to the
solution and subtracted from the experimental data.
The automatic iR-drop compensation facility was used
for all experiments. Bis(hydroxymethyl)ferrocene [25],
lithium diphenylphosphide [27] and bis(benzoni-
trile)dichloroplatinum(II) [28] were synthesized accord-
ing to literature methods.
Yield: 12.7 g (37%), MS (FD, 30 °C): m/z 421.9
[M+]. Anal. Calc. for C20H30FeO6·H2O (440.31): C,
54.56; H, 7.32. Found: C, 54.70; H, 7.35%. H-NMR
(CDCl3, 22 °C): l=3.4–3.6 (m, 16H, OCH2), 4.0–4.1
(m [29], 8H, Cp-H), 4.2 (s, 4H, FcCH2). 13C{1H}-NMR
(CDCl3, 22 °C): l=61.3 (CH2OH), 68.6 (2,2%-Fc),
68.8, 68.9 (OCH2CH2O), 69.6 (3,3%-Fc), 70.0 (FcCH2),
72.4 (CH2CH2OH), 83.5 (1,1%-Fc).
1
4.4. 1,1%-Bis(9-hydroxy-2,5,7-trioxanonyl)ferrocene (1b)
Yield: 22.8 g (55%), MS (FD, 30 °C): m/z 510.5
[M+]. Anal. Calc. for C24H38FeO8·H2O (528.42): C,
1
54.55; H, 7.63. Found: C, 54.17; H, 7.96%. H-NMR
(CDCl3, 22 °C): l=3.4–3.7 (m, 24H, OCH2), 3.9–4.0
(m [29], 8H, Cp-H), 4.1 (s, 4H, FcCH2). 13C{1H}-NMR
(CDCl3, 22 °C): l=61.0 (CH2OH), 68.5 (2,2%-Fc),
68.4, 68.5, 68.7, 69.8 (OCH2CH2O), 69.5 (3,3%-Fc), 70.1
(FcCH2), 72.2 (CH2CH2OH), 83.1 (1,1%-Fc).
4.5. 1,1%-Bis(11-hydroxy-2,5,7,9-tetraoxaundecyl)-
ferrocene (1c)
Yield: 16.3 g (34%), MS (FD, 30 °C): m/z 598.4
[M+]. Anal. Calc. for C28H46FeO10·H2O (616.52): C,
1
54.55; H, 7.85. Found: C, 55.24; H, 8.00%. H-NMR
(CDCl3, 22 °C): l=3.4–3.6 (m, 32H, OCH2), 4.0–4.1
(m [29], 8H, Cp-H), 4.2 (s, 4H, FcCH2). 13C{1H}-NMR
(CDCl3, 22 °C): l=61.1 (CH2OH), 68.6 (2,2%-Fc),
68.6, 68.8, 69.9, 70.0, 70.1 (OCH2CH2O), 69.6 (3,3%-Fc),
70.1 (FcCH2), 72.2 (CH2CH2OH), 83.3 (1,1%-Fc).
4.2. General procedure for the preparation of the diols
1a–c
In a 2000-ml three-necked flask sodium hydride (7.80
g, 325 mmol) was suspended in 400 ml of THF and the
appropriate oligoethyleneglycol (325 mmol) in 50 ml of
THF was slowly added at room temperature under
vigorous stirring. 1,1%-Bis(chloromethyl)ferrocene was
freshly prepared from 1,1%-bis(hydroxymethyl)ferrocene
(20.00 g, 81 mmol) with PCl3 (10.00 g, 73 mmol) and
pyridine (4 ml) in 400 ml of THF according to a
literature procedure [16]. The resulting solution was
transferred to a dropping funnel via a Teflon pipe
under an argon stream and was added drop-wise to the
above-mentioned suspension. The mixture was heated
to reflux for 12 h, then 500 ml of water was added and
the resulting solution was neutralized with 32% hydro-
chloric acid until pH 7 was achieved. The organic layer
was separated and the aqueous phase was extracted
with dichloromethane (5×100 ml). The combined or-
4.6. General procedure for the preparation of the
dimesylates 2a–c
Methanesulfonyl chloride (4.12 g, 36 mmol) dissolved
in 20 ml of dichloromethane was added drop-wise to a
solution of the appropriate diol 1a–c (12 mmol) and
triethylamine (4.61 g, 46 mmol) in 150 ml of
dichloromethane at 0 °C. The reaction mixture was
allowed to warm to room temperature, stirred for 2 h,
and hydrolyzed with 100 ml of a medium concentrated
aqueous NaHCO3 solution. The organic layer was sepa-
rated and the aqueous phase was extracted with
dichloromethane (3×20 ml). The combined organic
layers were dried with Na2SO4, filtered, and the solvent
was removed in vacuo to obtain the dimesylates 2a–c

E. Lindner et al. / Journal of Organometallic Chemistry 630 (2001) 266–274
271
as dark orange brown oils. Due to their instability, the
dimesylates 2a–c were immediately converted to the
diphosphines 3a–c as described below.
temperature, stirred for 1 h, and quenched with 50 ml
of degassed water. The organic layer was separated and
the aqueous phase was extracted with dichloromethane
(3×20 ml). The solvent of the combined organic
phases was removed under reduced pressure. The crude
product was purified by column chromatography (de-
gassed ethyl acetate–n-hexane 2:1, diameter/length of
column 2.5/30 cm).
4.7. 1,1%-Bis(7-methylsulfonyloxy-2,5-dioxaheptyl)-
ferrocene (2a)
MS (FD, 30 °C): m/z 578.3 [M+]. IR (CH2Cl2):
w(OSO2CH3)=1177, 1357 cm−1 1H-NMR (CDCl3,
.
22 °C): l=3.0 (s, 6H, OSO2CH3), 3.4–3.6 (m, 8H,
OCH2CH2O), 3.7 (t, J(HH)=4.3 Hz, 4H, CH2CH2-
4.11. 1,1%-Bis(7-diphenylphosphinyl-2,5-dioxaheptyl)-
ferrocene (3a)
3
OSO2CH3), 4.0–4.1 (m [29], 8H, Cp-H), 4.2 (s, 4H,
FcCH2), 4.3 (t, 3J(HH)=4.3 Hz, 4H, CH2CH2-
OSO2CH3). 13C{1H}-NMR (CDCl3, 22 °C): l=37.0
(OSO2CH3), 68.3 (2,2%-Fc), 68.6, 68.7 (OCH2CH2O),
68.8 (CH2CH2OSO2CH3), 69.2 (CH2CH2OSO2CH3),
69.6 (3,3%-Fc), 70.0 (FcCH2), 83.2 (1,1%-Fc).
Yield: 5.9 g (65% based on 1a). MS (FD, 30 °C): m/z
758.3 [M+]. Anal. Calc. for C44H48FeO4P2 (758.65): C,
69.66; H, 6.38. Found: C, 69.70; H, 6.54%. 31P{1H}-
NMR (CDCl3, 22 °C): l= −21.2 (s). 1H-NMR
(CDCl3, 22 °C): l=2.3 (m, 4H, CH2P), 3.4–3.5 (m,
12H, OCH2), 4.0–4.1 (m [29], 8H, Cp-H), 4.2 (s, 4H,
FcCH2), 7.2–7.4 (m, 20H, Ph). 13C{1H}-NMR (CDCl3,
4.8. 1,1%-Bis(9-methylsulfonyloxy-2,5,7-trioxanonyl)-
ferrocene (2b)
1
22 °C): l=28.6 (d, J(PC)=12.8 Hz, CH2P), 68.4 (d,
2J(PC)=25.6 Hz, CH2CH2P), 68.9 (2,2%-Fc), 68.8, 69.2
(OCH2CH2O), 69.9 (3,3%-Fc), 70.0 (FcCH2), 83.5 (1,1%-
Fc), 128.3 (p-Ph), 128.4 (d, 3J(PC)=7.1 Hz, m-Ph),
MS (FD, 30 °C): m/z 565.5 [M+]. IR (CH2Cl2):
w(OSO2CH3)=1177, 1355 cm−1 1H-NMR (CDCl3,
.
22 °C): l=3.0 (s, 6H, OSO2CH3), 3.4–3.6 (m, 8H,
OCH2CH2O), 3.7 (t, 3J(HH)=4.4 Hz, 4H,
CH2CH2OSO2CH3), 4.0–4.1 (m [29], 8H, Cp-H), 4.2 (s,
4H, FcCH2), 4.3 (t, 3J(HH)=4.4 Hz, 4H,
CH2CH2OSO2CH3). 13C{1H}-NMR (CDCl3, 22 °C):
l=37.4 (OSO2CH3), 68.8 (2,2%-Fc), 68.7, 68.8, 68.9,
69.0 (OCH2CH2O), 69.2 (CH2CH2OSO2CH3), 69.8
(3,3%-Fc), 70.0 (FcCH2), 70.2 (CH2CH2OSO2CH3), 83.3
(1,1%-Fc).
2
1
132.6 (d, J(PC)=18.5 Hz, o-Ph) 138.1 (d, J(PC)=
12.1 Hz, ipso-Ph).
4.12. 1,1%-Bis(9-diphenylphosphinyl-2,5,7-trioxanonyl)-
ferrocene (3b)
Yield: 5.7 g (56% based on 1b). MS (FD, 30 °C): m/z
846.3 [M+]. Anal. Calc. for C48H56FeO6P2 (846.76): C,
68.09; H, 6.67. Found: C, 68.14; H, 6.26%. 31P{1H}-
NMR (CDCl3, 22 °C): l= −21.1 (s). 1H-NMR
(CDCl3, 22 °C): l=2.3 (m, 4H, CH2P), 3.5–3.6 (m,
20H, OCH2), 4.0–4.1 (m [29], 8H, Cp-H), 4.2 (s, 4H,
FcCH2), 7.2–7.4 (m, 20H, Ph). 13C{1H}-NMR (CDCl3,
4.9. 1,1%-Bis(11-methylsulfonyloxy-2,5,7,9-
tetraoxaundecyl)ferrocene (2c)
MS (FD, 30 °C): m/z 754.3 [M+]. IR (CH2Cl2):
1
w(OSO2CH3)=1171, 1344 cm−1 1H-NMR (CD2Cl2,
.
22 °C): l=28.7 (d, J(PC)=13.2 Hz, CH2P), 68.4 (d,
2J(PC)=25.3 Hz, CH2CH2P), 68.9 (2,2%-Fc), 68.9, 69.1,
70.4, 70.5 (OCH2CH2O), 69.9 (3,3%-Fc), 70.0 (FcCH2),
22 °C): l=3.0 (s, 6H, OSO2CH3), 3.5–3.6 (m, 8H,
OCH2CH2O), 3.7 (t, 3J(HH)=4.2 Hz, 4H,
CH2CH2OSO2CH3), 4.1–4.2 (m [29], 8H, Cp-H), 4.2 (s,
4H, FcCH2), 4.3 (t, 3J(HH)=4.2 Hz, 4H,
CH2CH2OSO2CH3). 13C{1H}-NMR (CD2Cl2, 22 °C):
l=37.3 (OSO2CH3), 68.8 (2,2%-Fc), 68.7, 68.9, 69.1,
69.5, 69.6 (OCH2CH2O), 69.8 (3,3%-Fc), 70.2 (FcCH2),
70.3 (CH2CH2OSO2CH3), 70.4 (CH2CH2OSO2CH3),
83.7 (1,1%-Fc).
3
83.6 (1,1%-Fc), 128.4 (d, J(PC)=6.8 Hz, m-Ph), 128.5
(p-Ph), 132.6 (d, 2J(PC)=18.9 Hz, o-Ph) 138.7 (d,
1J(PC)=12.5 Hz, ipso-Ph).
4.13. 1,1%-Bis(11-diphenylphosphinyl-2,5,7,9-
tetraoxaundecyl)ferrocene (3c)
Yield: 6.7 g (60% based on 1c). MS (FD, 30 °C): m/z
934.2 [M+]. Anal. Calc. for C52H64FeO8P2 (934.88): C,
66.81; H, 6.90. Found: C, 66.84; H, 6.79. 31P{1H}-
NMR (CDCl3, 22 °C): l= −21.1 (s). 1H-NMR
(CDCl3, 22 °C): l=2.3 (m, 4H, CH2P), 3.4–3.5 (m,
28H, OCH2), 4.0–4.1 (m [29], 8H, Cp-H), 4.2 (s, 4H,
FcCH2), 7.2–7.4 (m, 20H, Ph). 13C{1H}-NMR (CDCl3,
4.10. General procedure for the preparation of the
bisphosphines 3a–c
A freshly prepared solution of lithium diphenylphos-
phide (6.92 g, 36 mmol) in 50 ml of THF was added
drop-wise to a solution of the corresponding dimesylate
2a–c, prepared as described above, in 150 ml of THF
at 0 °C. The solution was allowed to warm to room
1
22 °C): l=28.5 (d, J(PC)=12.8 Hz, CH2P), 68.3 (d,
2J(PC)=25.6 Hz, CH2CH2P), 68.7 (2,2%-Fc), 68.8, 69.0,

272
E. Lindner et al. / Journal of Organometallic Chemistry 630 (2001) 266–274
70.3, 70.4 (OCH2CH2O), 69.7 (3,3%-Fc), 69.9 (FcCH2),
m-Ph), 129.9 (m [30], N=63.0 Hz, ipso-Ph), 130.7
(p-Ph), 133.2 (m [30], N=10.3 Hz, o-Ph). 195Pt{1H}-
NMR (CDCl3, 22 °C): l= −4399 (t, J(PtP)=3632
3
83.4 (1,1%-Fc), 128.2 (d, J(PC)=6.4 Hz, m-Ph), 128.4
(p-Ph), 132.4 (d, 2J(PC)=19.2 Hz, o-Ph) 138.0 (d,
1J(PC)=12.8 Hz, ipso-Ph).
1
Hz).
4.14. General procedure for the preparation of the
polyoxadiphosphaplatinaferrocenophanes 4a–c
4.17. 15,15-Dichloro-2,5,8,11,19,22,25,28-octaoxa-
14,14,16,16-tetraphenyl-14,16-diphospha-15-platina-
[29]ferrocenophane (4c)
Solutions of (PhCN)2PtCl2 (1.18 g, 2.5 mmol) and of
the appropriate bisphosphine (2.5 mmol) in 200 ml of
dichloromethane were simultaneously added drop-wise
during 12 h at room temperature to 500 ml of stirred
dichloromethane. After stirring for additional 3 h, the
solvent was removed under reduced pressure and the
residue was purified by column chromatography (de-
gassed dichloromethane–ethyl acetate 2:1, diameter/
length of column 2.5/30 cm). The polyoxadi-
phosphaplatinaferrocenophanes were obtained from the
first fraction as bright yellow powders.
Yield: 0.54 g (18%); m.p. 135 °C. MS (FD, 30 °C):
m/z 1199.9 [M+]. Anal. Calc. for C52H64Cl2FeO8-
Table 2
Crystal data and structure refinement for 4a
Empirical formula
Formula weight
Temperature (K)
C44H48Cl2FeO4P2Pt
1024.64
298(2)
,
Wavelength Mo–Ka (A)
Crystal system
0.71073
Triclinic
(
Space group
Unit cell dimensions
P1
4.15. 9,9-Dichloro-2,5,13,16-tetraoxa-8,8,10,10-
tetraphenyl-8,10-diphospha-9-platina-[17] ferro-
cenophane (4a)
,
a (A)
21.990(4)
29.865(6)
29.877(6)
101.72(3)
108.69(3)
108.66(3)
16 557(6)
16
,
b (A)
,
c (A)
a (°)
i (°)
Yield: 1.43 g (56%); m.p. 196 °C (dec.). MS (FD,
30 °C): m/z 1024.0 [M+]. Anal. Calc. for
C44H48Cl2FeO4P2Pt (1024.64): C, 51.58; H, 4.72; Cl,
6.92. Found: C, 51.33; H, 4.72; Cl, 7.15%. 31P{1H}-
k(°)
3
,
V (A )
Z
Dcalc (g cm−3
)
1.644
0.3×0.3×0.2
3.97
Crystal size (mm3)
1
NMR (CDCl3, 22 °C): l=4.3 (sd, J(PtP)=3632 Hz).
Absorption coefficient
1H-NMR (CDCl3, 22 °C): l=2.4 (m, 4H, CH2P), 3.6
(m, 8H, OCH2CH2O), 3.9 (m, 4H, OCH2CH2P), 4.1–
4.2 (m [29], 8H, Cp-H), 4.3 (s, 4H, FcCH2), 7.1–7.5 (m,
20H, Ph). 13C{1H}-NMR (CDCl3, 22 °C): l=27.1 (m
[30], N=40.9 Hz, CH2P), 67.2 (CH2CH2P), 68.1 (2,2%-
Fc), 68.9, 69.5 (OCH2CH2O), 69.4 (3,3%-Fc), 70.4
(FcCH2), 85.0 (1,1%-Fc), 128.1 (m [30], N=11.0 Hz,
m-Ph), 130.6 (p-Ph), 131.4 (m [30], N=63.7 Hz, ipso-
Ph), 133.1 (m [30], N=10.0 Hz, o-Ph). 195Pt{1H}-NMR
(mm−1
)
F(000)
65 552
2.17–25.92
q Range for data collection
(°)
Data reduction/correction
Reflections collected
Independent reflections
Completeness to q=25.92°
Index ranges
Background, Polarisation, Lorentz
218 042
58 730 (Rint=0.1122)
91.1%
−265h526, −335k533,
−365l536
Refinement method
Full-matrix-block least-squares on
1
(CDCl3, 22 °C): l= −4400 (t, J(PtP)=3632 Hz).
F2
Data/restraints/parameters
Goodness-of-fit
Final R-indices [I\2|(I)]
R indices (all data)
Max. shift/esd
58 730/14/1963
1.579
R1=0.0800; wR2=0.2064
R1=0.1847, wR2=0.2439
B0.0005
4.16. 12,12-Dichloro-2,5,8,16,19,22-hexaoxa-
11,11,13,13-tetraphenyl-11,13-diphospha-12-platina-
[23]ferrocenophane (4b)
Largest diff. peak and hole
2.556 and −3.269
Yield: 0.53 g (19%); m.p. 95 °C. MS (FD, 30 °C):
m/z 1112.2 [M+]. Anal. Calc. for C48H56Cl2FeO6P2Pt
(1112.76): C, 51.81; H, 5.07; Cl, 6.37. Found: C, 51.92;
H, 5.24; Cl, 6.40%. 31P{1H}-NMR (CDCl3, 22 °C):
l=5.4 (sd, 1J(PtP)=3632 Hz). 1H-NMR (CDCl3,
22 °C): l=2.5 (m, 4H, CH2P), 3.4–3.6 (m, 16H,
OCH2CH2O), 3.8 (m, 4H, OCH2CH2P), 4.0–4.1 (m
[29], 8H, Cp-H), 4.2 (s, 4H, FcCH2), 7.1–7.5 (m, 20H,
Ph). 13C{1H}-NMR (CDCl3, 22 °C): l=28.9 (m [30],
N=39.1 Hz, CH2P), 67.0 (CH2CH2P), 68.5 (2,2%-Fc),
69.0, 69.4, 70.3, 70.6 (OCH2CH2O), 69.5 (3,3%-Fc), 70.1
(FcCH2), 84.4 (1,1%-Fc), 128.1 (m [30], N=11.0 Hz,
−3
(e−
A
)
,
% ꢀꢀFoꢀ−ꢀFcꢀꢀ
R1=hkl
% ꢀFoꢀ
hkl
%w(F2o−F2c)2
D
hkl %w(F2o)2
wR2=
hkl
%w(F2o−F2c)2
D
hkl
N
obs−Nparameter
Goodness of fit=

E. Lindner et al. / Journal of Organometallic Chemistry 630 (2001) 266–274
273
P2Pt·2H2O (1236.88): C, 50.50; H, 5.54; Cl, 5.73.
Found: C, 50.58; H, 5.37; Cl, 5.46%. 31P{1H}-NMR
References
1
1
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[30], N=42.0 Hz, CH2P), 67.1 (CH2CH2P), 68.8 (2,2%-
Fc), 69.2, 69.4, 70.1, 70.7 (OCH2CH2O), 69.7 (3,3%-Fc),
70.4 (FcCH2), 84.1 (1,1%-Fc), 128.3 (m [30], N=11.0
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thoroughly selected crystal was transferred to a glass
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absorption correction was applied. Cell parameters and
refinement details are summarized in Table 2. The data
(
fits best with the triclinic space group P1 with eight
independent molecules per unit cell (Z=16). The struc-
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Crystallographic data for the structural analysis have
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Data Centre CCDC no. 158649. Copies of this informa-
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CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(Fax: +44-1223-336033; e-mail: deposit@ccdc.cam.
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chen Industrie is gratefully acknowledged. Degussa AG
is thanked for supplying starting materials. Dipl.-Chem.
S. Buchmann, Institut fu¨r Organische Chemie, Univer-
sity of Tu¨bingen, is gratefully thanked for the CV
measurements. Professor Dr H.-J. Meyer, Institut fu¨r
Anorganische Chemie I, University of Tu¨bingen, is
thanked for providing the single crystal diffractometer.

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