Calix[4]arene-derived diphosphines, diphosphinites and diphosphites as chelating ligands for transition metal ions. Encapsulation of silver(I) in a calix-crown diphosphite

Article abstract of DOI:10.1039/b009005k

A series of lower rim-functionalised calix[4]arenes bearing 1,3-positioned phosphorus(III) ligands L¹-L⁹ have been synthesized and their coordinative properties examined. L¹ and L² {5,11,17,23-tetra-tert-butyl-25,27-bis[2-(diphenylphosphino) ethoxy]- and -25,27-bis(diphenylphosphinomethoxy)-26,28-bis(3-oxabutyloxy)calix[4]arene} react with [Rh(nbd)(THF)₂]BF₄ (nbd = 1,5-norbornadiene; THF = tetrahydrofuran) to afford in high yield the complexes [Rh(nbd)L ¹]BF₄ and [Rh(nbd)L²]BF₄, respectively, where the calixarene behaves as a P,P′ chelator. Both complexes catalyse hydroformylation of styrene at comparable rates, the linear:branched aldehyde ratio being 5:95. The presence of the ether side groups did not exert a noticeable effect on the selectivity nor the catalytic activity. Reaction of L¹-L⁸ with [Pd(η³- C₃H₄Me)(THF)₂]BF₄ gave the corresponding cationic chelate complexes [Pd(η³-C ₃H₄Me)Lⁱ]BF₄ that are active in the catalytic alkylation of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate. Owing to the presence of a non-planar Pd-allyl fragment, the achiral calixarene subunits of some of these complexes are no longer C_2v-symmetrical, as evidenced by the ¹H and ¹³C NMR spectra that show non-equivalent side groups. Selective chelation via the two phosphorus atoms was also observed in the complexes [RuCl(p-MeC₆H₄Pr ⁱ)Lⁱ]BF₄ (Lⁱ = L³ or L⁴) obtained by reaction of the amide phosphines Li with [RuCl(p-MeC₆H₄Prⁱ)(THF)₂]BF ₄ [L³ = 5,11,17,23-tetratert-butyl-25,27- bis(diethylcarbamoylmethoxy)-26,28-bis(diphenylphosphinomethoxy)- and L ⁴ = 5,11,17,23-tetratert-butyl-25,27-bis(diphenylphosphinomethoxy)- 26,28-bis{(1-(R)-phenylethyl)carbamoylmethoxy}-calix[4]arene]. Reaction of L³ or L⁴ with neutral [RuCl₂(p-MeC ⁶H₄Pri)]₂ afforded the bimetallic complexes [{RuCl(p-MeC₆H₄Pri)}₂-Lⁱ] where the calixarene acts as a P,P′ bridging ligand. Reaction of AgBF₄ with calix-crown L⁹ {25,27-bis(diethoxyphosphinoxy)-26,28-(3,6,9- trioxaundecane-1,11-dioxy)calix[4]arene} resulted in quantitative formation of the complex [AgL⁹]BF₄ in which the silver(I) ion lies inside the cavity constituted by the crown ether fragment and the two phosphorus arms. As revealed by a single crystal X-ray diffraction study, the Ag ⁺ ion has a trigonal P₂O coordination environment with a P-Ag-P angle of 134.74(4)°. The Royal Society of Chemistry 2001.

Full text of DOI:10.1039/b009005k

View Article Online / Journal Homepage / Table of Contents for this issue
Calix[4]arene-derived diphosphines, diphosphinites and diphosphites
as chelating ligands for transition metal ions. Encapsulation of
silver(I) in a calix-crown diphosphite
Catherine Jeunesse, Cedric Dieleman, Stéphane Steyer and Dominique Matt*
Université Louis Pasteur, Laboratoire de Chimie Inorganique Moléculaire, UMR 7513 CNRS,
1, rue Blaise Pascal, F-67008 Strasbourg Cedex, France
Received 8th November 2000, Accepted 19th January 2001
First published as an Advance Article on the web 19th February 2001
A series of lower rim-functionalised calix[4]arenes bearing 1,3-positioned phosphorus() ligands L1–L9 have been
synthesized and their coordinative properties examined. L1 and L2 {5,11,17,23-tetra-tert-butyl-25,27-bis[2-(diphenyl-
phosphino)ethoxy]- and -25,27-bis(diphenylphosphinomethoxy)-26,28-bis(3-oxabutyloxy)calix[4]arene} react with
[Rh(nbd)(THF)2]BF4 (nbd = 1,5-norbornadiene; THF = tetrahydrofuran) to afford in high yield the complexes
[Rh(nbd)L1]BF4 and [Rh(nbd)L2]BF4, respectively, where the calixarene behaves as a P,PЈ chelator. Both complexes
catalyse hydroformylation of styrene at comparable rates, the linear : branched aldehyde ratio being 5 : 95. The
presence of the ether side groups did not exert a noticeable effect on the selectivity nor the catalytic activity. Reaction
of L1–L8 with [Pd(η3-C3H4Me)(THF)2]BF4 gave the corresponding cationic chelate complexes [Pd(η3-C3H4Me)Li]BF4
that are active in the catalytic alkylation of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate. Owing to the
presence of a non-planar Pd–allyl fragment, the achiral calixarene subunits of some of these complexes are no longer
C2v-symmetrical, as evidenced by the 1H and 13C NMR spectra that show non-equivalent side groups. Selective
chelation via the two phosphorus atoms was also observed in the complexes [RuCl(p-MeC6H4Pri)Li]BF4 (Li = L3 or
L4) obtained by reaction of the amide phosphines Li with [RuCl(p-MeC6H4Pri)(THF)2]BF4 [L3 = 5,11,17,23-tetra-
tert-butyl-25,27-bis(diethylcarbamoylmethoxy)-26,28-bis(diphenylphosphinomethoxy)- and L4 = 5,11,17,23-tetra-
tert-butyl-25,27-bis(diphenylphosphinomethoxy)-26,28-bis{(1-(R)-phenylethyl)carbamoylmethoxy}-calix[4]arene].
Reaction of L3 or L4 with neutral [RuCl2(p-MeC6H4Pri)]2 afforded the bimetallic complexes [{RuCl(p-MeC6H4Pri)}2-
Li] where the calixarene acts as a P,PЈ bridging ligand. Reaction of AgBF4 with calix-crown L9 {25,27-bis(diethoxy-
phosphinoxy)-26,28-(3,6,9-trioxaundecane-1,11-dioxy)calix[4]arene} resulted in quantitative formation of the
complex [AgL9]BF4 in which the silver() ion lies inside the cavity constituted by the crown ether fragment and the
two phosphorus arms. As revealed by a single crystal X-ray diffraction study, the Agϩ ion has a trigonal P2O
coordination environment with a P–Ag–P angle of 134.74(4)Њ.
Calix[4]arenes (A) continue to attract considerable attention in
synthetic chemistry, notably as platforms for the build-up of
sophisticated molecular cages and claw-like ligands.1,2 Such
architectures have been exploited in recent years for producing
a number of compounds of practical interest, in particular
ion-selective receptors,3–7 molecular sensors,8–12 homogeneous
catalysts13–15 and highly ordered materials.16,17
In the last decade several research groups have reported on
the phosphorus functionalisation18 of calixarenes and initiated
the co-ordination chemistry of some phosphorus() deriv-
atives.19–26 Our group was mainly involved in the design and
study of conical calix[4]arenes bearing two phosphine ligands
tethered at distal phenol units.21,27–29 We found that, towards
transition metals, these diphosphines usually behave as
chelators resulting in the formation of complexes (B) where the
metal centre is located at the entrance of the calixarene cavity.
Functional groups can be introduced on the adjacent phenol
units in order to control the degree of encapsulation of the
chelated metal atom. In such complexes the side groups are
expected to exert a critical steric control on a reaction taking
place at the metal centre and, for example, favour shape-
selective reactions or induce enantioselectivity. When the
diphosphine acts as a trans spanning ligand the whole ligand
behaves as a so-called hemispherical diphosphine30 (C) in which
the cavity blocks a half-space about the chelated metal centre.
In the present study we report synthetic methodology leading
to transition metal chelate complexes starting from calix[4]-
arenes that are distally substituted by phosphorus arms of
various lengths. The calixarenes also contain auxiliary func-
tions, including chiral groups, that may display coordinating
behaviour. Particular attention is paid to possible steric or
DOI: 10.1039/b009005k
J. Chem. Soc., Dalton Trans., 2001, 881–892
This journal is © The Royal Society of Chemistry 2001
881

View Article Online
binding interactions between the auxiliary groups and the metal
centre, in particular in some palladium–allyl complexes. We
also describe the crystal structure of a silver() complex contain-
ing a diphosphite ligand built on a 1,3-calix[4]arene crown-5
matrix (crown-52 represents a bridging O(CH2CH2O)5 unit).
chiral diphosphine L5 (Scheme 2). The synthesis of L5 starts
with the introduction of a methoxyethyl group followed by
attachment of a chiral (R)-CH2C(O)NHCH(Me)Ph substitu-
ent on the distal phenolic position (see Experimental section).
The two CH2PPh2 groups were then introduced in a single step
as phosphine oxides, employing TsOCH2P(O)Ph2. High yield
reduction of the phosphine oxide moieties was achieved in a
refluxing PhSiH3–toluene mixture. As expected, owing to the
presence of an asymmetric carbon atom in L5, the four
ArCH2Ar bridges appear as four distinct AB patterns in the 1H
NMR spectrum. The chemical shifts of the corresponding 13C
carbon atoms are consistent with a cone conformation.
Preparation of diphosphinite L7 was achieved by treating the
dihydroxy precursor L1a with n-BuLi followed by addition of
Ph2PCl in THF. Compound L8 has been described previously.27
Diphosphite L9 was readily prepared using n-BuLi–THF and
PCl(OEt)2 (see Experimental section). The phosphite signal
was found at δ 140.0 in the 31P NMR spectrum. All important
spectroscopic data for L1–L9 are reported in the Experimental
section.
Results and discussion
Synthesis of calix-phosphines
The P,P-chelators used for the present study, L1–L9, differ from
each other in the length of the two pendant phosphine ligands
tethered to the calix platform as well as in the nature of the
adjacent groups. The phosphorus atoms are either directly con-
nected to the phenolic oxygen atoms (phosphinites L7 and L8
and phosphite L9) or separated from these by CH2CH2 (phos-
phine L1) or CH2 spacers (phosphines L2–6). The neighbouring
auxiliary functions bear oxygen atoms of various donor
strengths, namely ethers, esters and amides, some of them (L4–6
L8) being linked to chiral groups.
,
Preparation of rhodium(I), palladium(II), ruthenium(II), and
silver(I) chelate complexes
All ligands employed in this study comprise two phosphorus
atoms that are separated by relatively long spacers comprising
11–15 atoms. Such diphosphines may therefore, a priori, either
lead to mononuclear chelate complexes or form polynuclear
complexes where the ligand behaves as a bridging ligand.
Examples of the latter type have recently been found in our
group.27 We have now found that a convenient method that
favours chelating behaviour over oligomer formation consists in
treating such diphosphines with precursors containing weak
donors, typically cationic species stabilised by solvent mole-
cules, so as to facilitate fast binding of both phosphorus()
centres at the same metal. Most complexes outlined below were
obtained according to this strategy. It is noteworthy that this
methodology does not require that the reaction be carried out
under high dilution conditions.
Treatment of [RhCl(nbd)]2 (nbd = norbornadiene) in CH2Cl2
with AgBF4 followed by reaction of the resulting cationic
species with L1 afforded complex 2 in high yield. There was no
indication for oligomer formation. The FAB MS spectrum of 2
shows an intense peak at m/z = 1383 (with the expected isotopic
profile) corresponding to the [RhL1]ϩ ion. The NMR spectra
are in keeping with a C2v-symmetrical structure. The expected
cis stereochemistry about Rh was confirmed by the 31P NMR
spectrum (doublet at δ 16.3 with J(RhP) = 153 Hz) which
is consistent with those reported for other cis-[Rh(nbd)-
(diphosphine)]ϩ complexes.34 Complex 3 was obtained in high
yield using conditions similar to those employed for 2, but
starting from L2.
The rhodium complexes 2 and 3 display comparable catalytic
activity in styrene hydroformylation (turnover frequency,
TOF = ca. 7 hϪ1). Thus, operating at a temperature of 40 ЊC and
under a CO–H2 (1 : 1) pressure of 40 bar, 2-phenylpropanal and
3-phenylpropanal were formed in a 95 : 5 ratio (see Experi-
mental section). This high regioselectivity in favour of the
branched aldehyde is not unusual for rhodium phosphine com-
plexes.35 The activity being similar to that of other cationic
[Rh(diphosphine)(S)2]ϩ (s = solvent) complexes, it must be con-
cluded that the pendant ether groups do not behave as transient
ligands during the catalytic process. It should be remembered
here that hemilabile36 ether phosphines37 as well as mixed
phosphine oxide–phosphines38,39 have recently been shown to
enhance the reactivity of rhodium catalysed methanol carbon-
ylation when compared with related, PPh3-based systems.
The cationic palladium complexes 4–11 were readily formed
by treating [Pd(η3-C3H4Me)(THF)2]BF4 (obtained by reaction
of AgBF4 with [Pd(η3-C3H4Me)Cl]2 in THF) with the corre-
The calixarene with the longest dangling phosphorus ligands
is L1. This compound, presented here for the first time, was
prepared in 40% overall yield starting from p-tert-butyl-
calix[4]arene (1) according to Scheme 1. The introduction of
the phosphino groups was achieved by treating the PPh2Ϫ anion
with the ditosylated intermediate L1d (see Experimental
section). A similar strategy for tethering CH2CH2PPh2 groups
has been employed by the Reinhoudt group for a related calix-
arene.31 Phosphine L1 possesses the expected cone conform-
1
ation, as deduced from the H and 13C NMR spectra.32,33 The
phosphorus atoms appear as a single peak (at δ Ϫ23.4) in the
31P NMR spectrum. It should be emphasised here that attempts
to generate L1 by treating TsOCH2CH2P(O)Ph2 (Ts = p-Me-
C6H4SO2) with the corresponding doubly deprotonated calix-
arene were unsuccessful. In this case TsOH elimination occurs
which is followed by polymerisation of the resulting alkene.
The general strategy used for the preparation of the diphos-
phines L2–L6, bearing the shorter CH2PPh2 arms, has been
reported in a previous work,23 and is exemplified by the new
882
J. Chem. Soc., Dalton Trans., 2001, 881–892

View Article Online
Scheme 1 Stepwise build-up of diphosphine L1.
Scheme 2 Synthesis of the chiral diphosphine L5.
sponding phosphorus() ligands. All complexes were charac-
1
terised by H, 13C and 31P NMR and elemental analysis. The
formation of chelate complexes was unambiguously inferred
from FAB mass spectra which all show the corresponding
[PdL(C3H4Me)]ϩ peak. In almost all 1H NMR spectra the Hanti
and Hsyn protons of the allylic part could be identified, and in
each case were found to give distinct signals, indicating that,
where present, allyl rotation is slow on the NMR timescale. As
in other PdII–diphosphine complexes bearing a slowly rotating
allyl ligand, the two half spaces defined by the metal plane are
equivalent CH2CH2OMe groups. We anticipated that for 10,
where the allyl/methoxy proximity is the highest, the two OMe
groups would be significantly differentiated. This is indeed the
case. Thus, the methoxy signal separation is 0.18 ppm for
complex 10 vs. 0.00 and 0.02 ppm, respectively, for 4 and 5.
Clearly in 10 one side group comes close to the C3H4Me
fragment.
The complexes 7–9 contain chiral carbon atoms and hence
the corresponding 31P NMR spectra each display an AB
pattern. The J(PP) coupling constant of ca. 40 Hz confirms the
cis arrangement of the two phosphorus atoms. The 31P NMR
spectrum of 11 which is also chiral shows only an A2 spec-
trum, probably accidentally, but as expected the two menthyl
1
non-equivalent. This asymmetry becomes evident in some H
NMR spectra showing that the calixarene units no longer retain
1
the C2v symmetry of the ligand. For example, the H NMR
spectrum of complex 6 displays two distinct amide groups
(Y in the drawing), two AB patterns for the ArCH2Ar groups
and three But signals (intensity 1 : 1 : 2). It is interesting that
(to the best of our knowledge) such spatial anisotropy has
not previously been detected in other [PdCl(C3H4Me)(L)]
complexes where L is an achiral phosphine. The same
asymmetry was also evident in complexes 4, 5 and 10 where the
metal centres are located in pockets constituted by two non-
J. Chem. Soc., Dalton Trans., 2001, 881–892
883

View Article Online
Table 1 Palladium catalysed alkylation of 1,3-diphenylprop-2-enyl
acetatea
Complex
Ligand
Reaction time/h
Turnoverb
4
7
L1
L4
L5
L6
L7
L8
5
3
5
3
4
4
20
33
20
33
25
25
8
9
10
11
a Reaction conditions: 1.2 mmol allyl acetate, 0.012 mmol catalyst, 2.4
mmol dimethyl malonate, 2.4 mmol NaH; Pd : allyl acetate : malonate
ratio = 1 : 100 : 200; T = 67 ЊC; solvent THF. b In mol per mol per h.
Fig. 1 Possible orientations of the allyl ligand in complex 8.
analysis, mass and multinuclear NMR spectroscopy. The only
symmetry element of this molecule is a plane that contains the
Ru–Cl bond and which bisects the P–Rh–P angle. Hence the
two amide groups are no longer equivalent, as confirmed by 1H
and 13C NMR. The chiral complex 13 was obtained in a similar
way starting from L4. The presence in the 1H NMR spectrum of
four AB systems for the ArCH2Ar groups as well as that of four
tert-butyl signals is consistent with a C1-symmetrical molecule.
As expected, the 31P NMR spectrum displays an AB spec-
trum(2J(pp) = 49 Hz). It is noteworthy that the reactions of L3
and L4 with [RuCl2(p-MeC6H4Pri)]2 in dichloromethane gave
quantitatively the dimetallic complexes 14 and 15, respectively,
Scheme 3(b), in which the amide side groups remain unbonded.
The reaction of [RuClL(p-MeC6H4Pri)] complexes with other
hybrid P,O phosphines results in loss of the arene fragment and
formation of P,O-chelate complexes.42
Molecular models and previous studies carried out in our
laboratory showed that calixarenes bearing two phosphino
groups directly appended to distal phenolic oxygen atoms
may form cis complexes,27 but are unsuitable for formation of
chelate complexes having a pure trans stereochemistry. Never-
theless, considering their size and backbone flexibility it may be
anticipated that complexes with P–M–P angles larger than 120Њ
can be obtained from such ligands. In order to assess their
potential bite angle, we investigated the complexing behaviour
of the calix-crown diphosphite L9 towards Agϩ. L9 may simply
be regarded as a variation of ligand L7 where the phosphorus
atoms bear small substituents (OEt) and the two side groups are
replaced by a single polyether chain that straps two opposing
fragments are non-equivalent in the 1H NMR spectrum. Inter-
estingly, the 31P NMR spectrum of complex 8 displays two AB
patterns (intensity 1 : 3) owing to the formation of two isomers
characterised by different orientations of the C3H4Me groups
(Fig. 1). The 1H NMR spectrum confirms this observation.
Complexes 4, 7–9 and 10 and 11 were assessed in allylic
alkylation catalysis. Dimethyl malonate was treated with 1,3-
diphenylprop-2-enyl acetate in the presence of NaH as base.
Using the reaction conditions outlined in Table 1, full conver-
sion of the substrate was observed after ca. 4 h. There are no
striking differences between these catalysts in terms of activity.
The turnover numbers were close to those observed for good,
conventional allylation catalysts.40 These findings show that the
palladium centre remains accessible to the substrate despite its
location inside a pocket. In terms of enantioselectivity, the
complexes tested did not fulfil our expectations. The low
enantiomeric excess (e.e.) of these reactions will be presented
elsewhere, together with results obtained for other chiral calix-
phosphines.41
A further example where the side groups of L3 are differenti-
ated upon complexation is shown in Scheme 3(a). Thus,
reaction of L3 with the cationic complex [RuCl(p-MeC6H4Pri)-
(THF)]BF4 afforded 12 that was characterized by elemental
884
J. Chem. Soc., Dalton Trans., 2001, 881–892

View Article Online
Table 2 Selected bond distances (Å) and angles (Њ) for complex 16
Ag–P
Ag–O(6)
Ag–O(5)
2.3785(8)
2.360(5)
2.591(2)
P–O(1)
P–O(2)
P–O(3)
1.612(2)
1.593(2)
1.592(2)
P–Ag–P
P–Ag–O(6)
O(1)–P–O(3)
134.74(4)
P–Ag–O(5)
O(1)–P–O(2)
O(2)–P–O(3)
139.4(5)
102.5(1)
107.5(1)
121.8(1)/103.4(1)a
102.5(1)
a The O(6) atom is disordered over two C2-symmetrical positions.
Fig. 2 Molecular structure of the silver() complex 16. The BF4Ϫ anion
is not shown.
Scheme 3 Formation of cationic (a) and neutral (b) ruthenium
In conclusion, we have shown that 1,3-disubstituted calix-
[4]arenes bearing PR2, CH2PPh2, or CH2CH2PPh2 substituents
readily form chelate complexes when exposed to starting com-
plexes that contain weak donor ligands. In the complexes thus
formed the presence of two side functions lying close to the
metal centre constitutes a useful tool for probing the local
symmetry about the metal. Interaction with the side group was
found in one instance, namely the calix-crown complex 16,
where the P,P-chelated silver ion interacts with the central
oxygen atom of the crown-5 bridge. The structural attributes of
diphosphite L9, as revealed by an X-ray diffraction study, show
that 1,3-calix diphosphites give access to chelating ligands
having a large bite angle. Futher studies will be aimed at
exploiting this latter feature.
complexes from calix diphosphines containing amide side groups.
phenol units. Silver() was chosen for its ability readily to
form [MP2]ϩ and [MP2(S)]ϩ complexes (P = phosphine; S = 2e
donor ligand), the latter providing access to a wide range of
P–M–P angles, usually lying between 120 and 180Њ. Reaction
of L9 with AgBF4 in THF afforded quantitatively complex 16.
Experimental
General procedures can be taken from ref. 33. Samples of
p-tert-butylcalix[4]arene 1,45 5,11,17,23-tetra-tert-butyl-25,27-
dihydroxy-26,28-bis(3-oxabutyloxy)calix[4]arene L1a,23 5,11,
17,23-tetra-tert-butyl-25,27-bis(diphenylphosphinomethoxy)-
26,28-bis(3-oxabutyloxy)calix[4]arene L2,23 5,11,17,23-tetra-
tert-butyl-25,27-bis(diethylcarbamoylmethoxy)-26,28-bis(di-
phenylphosphinomethoxy)calix[4]arene L3,34 5,11,17,23-tetra-
tert-butyl-25,27-bis(diphenylphosphinomethoxy)-26,28-bis{(1-
(R)-phenylethyl)carbamoylmethoxy}calix[4]arene] L4,34 (ϩ)-
(R)-2-bromo-N-(1-phenylethyl)acetamide,34 5,11,17,23-tetra-
tert-butyl-25,27-dihydroxy-26,28-bis{(1R,2S,5R)-menthyloxy-
carbonylmethoxy}calix[4]arene L6a,27 5,11,17,23-tetra-tert-
butyl-25,27-bis(diphenylphosphinooxy)-26,28-bis{(1R,2S,5R)-
menthyloxycarbonylmethoxy}calix[4]arene L8,27 25,27-dihy-
The mass spectrum shows an intense peak at m/z = 931.2 with
the isotopic profile exactly as expected for [AgL9]ϩ. The NMR
spectra indicate C2v symmetry for the molecule. Complexation
of silver was inferred from the 31P NMR spectrum that
displays two doublets centred at δ 105.9 (J(P–Ag107) = 778,
J(P–Ag109) = 900 Hz). A single crystal X-ray diffraction study
confirmed the chelating behaviour of the diphosphite (Fig. 2).
Important structural parameters are given in Table 2. The
molecule possesses a symmetry axis in the solid state. The silver
atom adopts a trigonal P2O stereochemistry, involving the
central O(6) atom of the crown-5 unit. The Ag–P bond lengths
are 2.378(1) Å, while the Ag–O(6) bond length is 2.360(5) Å.
The P(1)–Ag–P(2) angle of 134.74(4)Њ is not unusual for a tri-
gonal AgOP2 arrangement (P = monophosphine), but such
large bite angles have rarely been observed in diphosphine–
silver complexes.43 The fact that such an angle can be obtained
with L9 illustrates the flexibility of the calix[4]arene scaffold.
Notably, another calixarene diphosphite with a large natural
bite angle has recently been described by van Leeuwen and co-
workers, but in this case the ligand derives from calix[6]arene.44
droxy-26,28-(3,6,9-trioxaundecane-1,11-dioxy)calix[4]arene,46
48
Ph2P(O)CH2OTs,47 [RhCl(nbd)]2
[Pd(η3-C3H4Me)Cl]2,49
and [RuCl2(p-MeC6H4Pri)]2 50 were prepared by using literature
procedures.
Preparations
5,11,17,23-Tetra-tert-butyl-25,27-dihydroxy-26,28-bis(3-oxa-
butyloxy)calix[4]arene L1a. A suspension of p-tert-butylcalix-
[4]arene (5.000 g, 7.71 mmol) in acetonitrile (200 cm3) was
J. Chem. Soc., Dalton Trans., 2001, 881–892
885

View Article Online
stirred at room temperature overnight with K2CO3 (1.380 g,
10.01 mmol). 2-Bromoethyl methyl ether (2.36 g, 16.94 mmol)
was then added and the mixture refluxed for 3 d. Over this
period during which the formation of intermediate L5a could be
detected (see below) three portions of BrCH2CH2OMe (1.50
mmol for each) and K2CO3 (1.50 mmol) were added after 24, 36
and 60 h. The reaction was followed by TLC (Rf of starting
compound = 1; Rf (L5a) = 0.5; Rf (L1a) = 0; SiO2, CH2Cl2). After
filtration the solvent was removed in vacuo. The residue was
dissolved in CH2Cl2 (100 cm3) and the resultant solution
washed first with saturated NH4Cl–water (2 × 100 cm3), then
with water (100 cm3). The organic layer was dried over MgSO4.
After filtration, the purified product was precipitated with
EtOH to yield a white solid (4.4 g, 75%), mp 222–223 ЊC. IR:
(KBr) ν(OH) 3360–3314br; (toluene) ν(OH) 3394s and 3295s
cmϪ1. 1H NMR (CDCl3): δ 7.40 (s, 2H, OH), 7.15 and 7.06 (2s,
8H, m-H), 4.39 and 3.32 (AB spin system, 8H, ArCH2Ar,
2J = 12.9 Hz), 4.17 and 3.89 (2m, 8H, OCH2CH2O), 3.56 (s, 6H,
OCH3), 1.30 (s, 18H, C(CH3)) and 0.99 (s, 18H, C(CH3)).
13C-{1H} NMR (CDCl3): δ 150.28–116.50 (arom. C), 75.05 (s,
OCH2), 71.23 (s, OCH2), 59.10 (s, OCH3), 33.81 and 33.63 (2s,
C(CH3)), 31.50 (s, C(CH3)), 31.35 (s, ArCH2Ar) and 30.91 (s,
C(CH3)). MS(EI): m/z (%) 764.4(100) [Mϩ]. Found: C, 78.22;
H, 8.85. Calc. for C50H68O6: C, 78.49; H, 8.96%.
61.66 (s, OCH2), 58.54 (s, OCH3), 34.03 and 33.55 (2s, C(CH3)),
31.64 and 30.97 (2s, C(CH3)) and 30.46 (s, ArCH2Ar). MS(CI):
m/z (%) 852.5 (100) [Mϩ]. Found: C, 76.22; H, 8.95. Calc. for
C54H76O8: C, 76.02; H, 8.98%.
5,11,17,23-Tetra-tert-butyl-25,27-bis[2-{[(4-methylphenyl)-
sulfonyl]oxy}ethoxy]-26,28-bis(3-oxabutyloxy)calix[4]arene L1d.
To a solution of L1c (2.500 g, 2.90 mmol) in pyridine (10 cm3)
was added p-toluenesulfonyl chloride (1.106 g, 5.80 mmol) at
0 ЊC. The mixture was stored at 0 ЊC for 4 days. The mixture
was then poured into an ice-cold 2 M HCl solution (100 cm3)
and the precipitate formed filtered off. The product was taken
up with CH2Cl2 and washed with HCl (2 × 100 cm3), then with
brine (2 × 100 cm3). After drying over MgSO4 the solution was
concentrated under reduced pressure and addition of hexane
gave a white, microcrystalline product. Yield: 3.102 g, 92%. mp
78–79 ЊC. 1H NMR (CDCl3): δ 7.80 and 7.34 (AB spin system,
8H, OC6H4CH3, J(AB) = 8.2), 7.04 and 6.47 (2s, 8H, m-H), 4.66
2
(t, 4H, OCH2, J = 6.1), 4.31 and 3.07 (AB spin system, 8H,
ArCH2Ar, 2J = 12.8), 4.27 (t, 4H, OCH2, 3J = 5.2), 3.86 and 3.63
(2t, 8H, OCH2CH2OCH3, 3J = 4.0 Hz), 3.37 (s, 6H, OCH3), 2.47
(s, 6H, C6H4CH3), 1.31 (s, 18H, C(CH3)) and 0.83 (s, 18H,
C(CH3)). 13C-{1H} NMR (CDCl3): δ 153.50–124.54 (arom. C),
73.90, 71.40, 70.63 and 69.38 (4s, OCH2), 58.50 (s, OCH3),
33.95 and 33.47 (2s, C(CH3)), 31.56 and 31.01 (2s, C(CH3)),
30.79 (s, ArCH2Ar) and 21.60 (s, C6H4CH3). FAB mass spec-
trum: m/z (%) 1160.4(5) [Mϩ]. Found: C, 70.26; H, 7.45. Calc.
for C68H88O12: C, 70.31; H, 7.64%.
5,11,17,23-Tetra-tert-butyl-25,27-bis(ethoxycarbonylmeth-
oxy)-26,28-bis(3-oxabutyloxy)calix[4]arene L1b. A suspension
of L1a (5.000 g, 6.50 mmol) in DMF (200 cm3) was stirred at
room temperature for 2 h with NaH (0.784 g, 32.70 mmol;
freed from mineral oil by washings with THF and pentane).
Ethyl bromoacetate (5.458 g, 32.7 mmol) was then added and
the mixture stirred overnight at 60 ЊC. The solvent was removed
under reduced pressure, and the residue taken up with CH2Cl2
(200 cm3). After washing with saturated NH4Cl–water (3 × 200
cm3), then with brine (200 cm3), the organic layer was dried over
MgSO4. After filtration, the solvent was removed in vacuo and
the product precipitated with MeOH to yield L1b as a white
solid. Yield: 5.200 g, 85%. mp 132–133 ЊC. IR(KBr, cmϪ1):
ν(C᎐O) 1760s and 1725s. 1H NMR (CDCl ): δ 6.87 and 6.72 (2s,
5,11,17,23-Tetra-tert-butyl-25,27-bis[2-(diphenylphosphino)-
ethoxy]-26,28-bis(3-oxabutyloxy)calix[4]arene L1. To a solution
of Ph2PH (0.337 g, 1.8 mmol) in THF (10 cm3) was added
n-BuLi (1.2 cm3, 1.8 mmol, 1.5 M solution in hexane). The
Ph2PLi solution was then added to a solution of L1d (1.000 g,
0.86 mmol) in dry THF (100 cm3). The mixture was refluxed for
6 h. After cooling to room temperature the solvent was removed
in vacuo. The residue was taken up with CH2Cl2 and addition of
EtOH gave a white pure product. Yield: 0.720 g, 70%. mp 172–
173 ЊC. 1H NMR (CDCl3): δ 7.49–7.42 and 7.35–7.33 (2 broad
m, 20H, PPh2), 6.91 and 6.64 (2s, 8H, m-H), 4.36 and 3.07 (AB
spin system, 8H, ArCH2Ar, 2J = 12.8), 4.13 (t, 4H, OCH2,
3J = 6.1), 4.05–3.87 (two overlapping t, 8H, OCH2), 3.28 (s, 6H,
᎐
3
8H, m-H), 4.83 (s, 4H, OCH2CO2Et), 4.71 and 3.18 (AB spin
system,8H,ArCH2Ar,2J = 12.8),4.25(q,4H,OCH2CH3,3J = 7),
4.11 and 3.87 (2t, 8H, OCH2CH2O, 3J = 5.1), 3.45 (s, 6H,
OCH3), 1.31 (t, 6H, OCH2CH3, 3J = 7 Hz), 1.14 (s, 18H,
C(CH3)) and 1.04 (s, 18H, C(CH3)). 13C-{1H} NMR (CDCl3):
3
OCH3), 2.80 (t, 4H, PCH2, J = 8.2 Hz), 1.18 (s, 18H, C(CH3))
and 0.97 (s, 18H, C(CH3)). 13C-{1H} NMR (CDCl3): δ 153.50–
124.65 (arom. C), 72.50, 71.88, 71.58 and 71.33 (4 peaks,
OCH2), 58.65 (s, OCH3), 33.84 and 33.62 (2s, C(CH3)), 31.45
and 31.19 (2s, C(CH3)), 30.90 (s, ArCH2Ar), 28.46 (d, PCH2,
J(PC) = 13 Hz). 31P-{1H} NMR (CDCl3) δ Ϫ23.4 (s, PPh2).
Found: C, 78.59; H, 7.95. Calc. for C78H94O6P2: C, 78.76; H,
7.97%.
δ 170.70 (C᎐O), 153.10–124.84 (arom. C), 73.17 (s, OCH ),
᎐
2
71.91 (s, OCH2), 70.89 (s br, OCH2CO), 60.19 (s, OCH2CH3),
58.54 (s, OCH3), 33.77 and 33.66 (2s, C(CH3)), 31.34 and 31.27
(2s, C(CH3)), 30.94 (s, ArCH2Ar) and 14.1 (s, OCH2CH3).
MS(EI): m/z (%) 936.4(100) [Mϩ]. Found: C, 74.15; H, 8.87.
Calc. for C58H80O10: C, 74.33; H, 8.60%.
5,11,17,23-Tetra-tert-butyl-25,27-bis(2-hydroxyethoxy)-
26,28-bis(3-oxabutyloxy)calix[4]arene L1c. To a solution of L1b
(3.000 g, 3.2 mmol) in diethyl ether (150 cm3) was added LiAlH4
(0.970 g, 25.5 mmol) in small portions at Ϫ10 ЊC and the mix-
ture stirred overnight at room temperature. HCl (2 M) was
added carefully until a precipitate had formed and the diethyl
ether layer was separated. The precipitate was treated with
another portion of diethyl ether (150 cm3) and the two fractions
were dried over MgSO4. After filtration, the solvent was
removed under reduced pressure. The residue was taken up with
CH2Cl2 and addition of MeOH gave a white product. Yield:
2.300 g, 84%. mp 238–239 ЊC. IR (KBr, cmϪ1): ν(OH) 3447br.
1H NMR (CDCl3): δ 7.16 and 6.52 (2s, 8H, m-H), 4.92 (t, 2H,
5,11,17,23-Tetra-tert-butyl-25,26,27-trihydroxy-28-(3-oxa-
butyloxy)calix[4]arene L5a. A suspension of p-tert-butylcalix-
[4]arene (10.000 g, 15.41 mmol) in acetonitrile (200 cm3) was
stirred at room temperature for 2 h with K2CO3 (1.280 g, 9.24
mmol). 2-Bromoethyl methyl ether (2.140 g, 15.41 mmol) was
then added and the mixture refluxed for 5 days. During this
period several portions of BrCH2CH2OCH3 (1.0 mmol for each
addition) and K2CO3 (0.5 mmol) were added after 1, 2, 3, and
4 d reaction time. The reaction was followed by TLC [Rf = 1
(starting compound); 0.49 (L5a); 0 (L1a); SiO2, CH2Cl2] and
stopped when all the starting compound had been consumed.
The solvent was removed under reduced pressure, and the
residue taken up with CH2Cl2 (200 cm3). After washing with
saturated NH4Cl–water (3 × 200 cm3), then with brine (200
cm3), the organic layer was dried over MgSO4. After filtration,
the solvent was removed in vacuo and the product purified by
column chromatography (SiO2, CH2Cl2) to yield L5a as a white
solid (7.500 g, 69%); mp 260–261 ЊC. IR (toluene, cmϪ1): ν(OH)
3430 and 3290. 1H NMR (CDCl3): δ 10.31 (s, 1H, OH), 9.42 (s,
2
CH2OH, exchanges with D2O, J = 4), 4.45 and 3.18 (AB spin
system, 8H, ArCH2Ar, 2J = 12.8), 4.18–4.16 and 4.15–4.14 (2m,
8H, OCH2CH2OH), 3.95 and 3.75 (2t, 8H, OCH2CH2OCH3,
3J = 4.0 Hz), 3.42 (s, 6H, OCH3), 1.36 (s, 18H, C(CH3)) and
0.83 (s, 18H, C(CH3)). 13C-{1H} NMR (CDCl3): δ 153.84–124.76
(arom. C), 76.77 (s, OCH2), 74.78 (s, OCH2), 71.00 (s, OCH2),
886
J. Chem. Soc., Dalton Trans., 2001, 881–892

View Article Online
2H, OH), 7.19–7.00 (8H, m-H), 4.47 and 3.44 (AB spin system,
32.17 and 31.91 (s, ArCH2Ar), 31.40 and 31.20 (2s, C(CH3))
2
4H, ArCH2Ar, J = 13.1), 4.34 (m, 2H, OCH2), 4.30 and 3.41
and 21.72 (NHCHCH3Ph). 31P NMR (CDCl3): δ 26.8 and
24.4 (2s, PPh2). Found: C, 76.95; H, 7.18; N, 1.04. Calc. for
C83H95NO8P2: C, 76.89; H, 7.39; N, 1.08%.
2
(AB spin system, 4H, ArCH2Ar, J = 13.1 Hz), 4.00 (m, 2H,
OCH2), 3.59 (s, 3H, OCH3), 1.24 (s, 9H, C(CH3)) and 1.21 (s,
27H, C(CH3)). 13C-{1H} NMR (CDCl3): δ 148.03–125.65
(arom. C), 74.93 (s, OCH2), 71.30 (s, OCH2), 59.13 (s, OCH3),
34.22, 33.96 and 33.04 (3s, C(CH3)), 32.05 and 31.51 (2s, Ar-
CH2Ar), 31.50(brsignal, C(CH3))and31.27(s, C(CH3)). Found:
C, 79.53; H, 9.07. Calc. for C47H62O5: C, 79.85; H, 8.84%.
(R)-5,11,17,23-Tetra-tert-butyl-25,27-bis[diphenylphosphino-
methoxy]-26-(3-oxabutyloxy)-28-[(1-phenylethyl)carbamoyl-
methoxy]calix[4]arene L5. A suspension of L5c (3.5 g, 2.9 mmol)
in toluene (150 cm3) was stirred for 10 days at 80 ЊC in the
presence of PhSiH3 (2 cm3, 30 mmol). The solvent was removed
under reduced pressure, and the residue taken up with
CH2Cl2 (10 cm3). Addition of EtOH afforded the product as a
white solid. Yield: 2.5 g, 69%. mp 90–95 ЊC. IR (KBr, cmϪ1):
v(C᎐O) 1663s. 1H NMR (CDCl ): δ 7.83–7.17 (arom. H ϩ NH),
(R)-5,11,17,23-Tetra-tert-butyl-25,27-dihydroxy-26-(3-oxa-
butyloxy)-28-[(1-phenylethyl)carbamoylmethoxy]calix[4]arene
L5b. A suspension of L5a (6.500 g, 9.2 mmol) in acetonitrile (150
cm3) was stirred at room temperature for 2 h with K2CO3 (0.762
g, 5.5 mmol). (R)-(ϩ)-2-Bromo-N-(1-phenylethyl)acetamide
(2.200 g, 9.2 mmol) was then added and the mixture refluxed for
2 d. The solvent was removed under reduced pressure, and the
residue taken up with CH2Cl2 (200 cm3). After washing with
saturated NH4Cl–water (3 × 200 cm3), then with brine (200
cm3), the organic layer was dried over MgSO4. After filtration,
the solvent was removed in vacuo and the product purified by
column chromatography (Rf = 0.3, SiO2, CH2Cl2–MeOH 95 : 5
v/v). Yield: 6.500 g, 88%. mp 118–120 ЊC. IR (KBr, cmϪ1):
᎐
3
6.69–6.49 (8H, m-H), 5.23 (dq, AMX3 spin system, 1H,
NHCHMePh, 3J(AM) ≈ 3J(AX) = 7.5), 5.15 (s, 2H, PCH2),
5.08 (s, 2H, PCH2), 5.09, 4.45, 4.41, 4.40 (4d, 4H, axial
ArCHAr), 4.63 and 4.51 (AB spin system, OCH2C(O),
3
2J(AB) = 15), 3.93 (m, 2H, OCH2, J(HH) = 5.5), 3.70 (m, 2H,
3
OCH2, J(HH) = 5.5 Hz), 3.14 (s, 3H, OCH3), 3.06, 3.02, 2.97
and 2.92 (4d, 4H, equat. ArCHAr, av. J(HaxHeq) = 12.8), 1.48
(d, 1H, NHCHMePh, 2J = 7.5 Hz), 1.09, 1.07, 1.05 and 1.00 (4s,
36H, C(CH3)). 13C-{1H} NMR (CDCl ): δ 168.98 (C᎐O),
᎐
3
ν(C᎐O) 1684s and 1653s; (toluene) ν(OH) 3422s and 3298,
152.98–124.17 (arom. C), 75.40 (d, PCH2, J(PC) = 8 Hz), 73.85
(s, OCH2), 72.41 (s, OCH2), 71.30 (s, OCH2CO), 57.79
(s, OCH3), 47.69 (NHCH), 33.11 and 33.01 (2s, C(CH3)), 31.63
and 31.34 (2s, ArCH2Ar), 30.75 and 30.65 (2s, C(CH3)) and
20.52 (s, NHCHCH3Ph). 31P NMR (CDCl3): δ Ϫ21.4 (s, PPh2).
Found: C, 75.03; H, 6.59; N, 0.86. Calc. for C83H95NO6P2ؒ
CH2Cl2: C, 74.76; H, 7.24; N, 1.04%.
᎐
ν(C᎐O) 1697s and 1669s. 1H NMR (CDCl ): δ 9.11 (d, 1H, NH,
᎐
3
3J = 7.7), 7.53–6.79 (m, 13H, arom. H), 5.32 (dq, AMX3 spin
system, 1H, NHCHMePh, 3J(AM) ≈ 3J(AX) = 7.0), 4.52 (s, 2H,
OCH2C(O)), 4.41, 4.34, 4.24, 4.15 (4d, 4H, axial ArCHAr),
4.11 (m, 2H, OCH2), 3.54 (m, 2H, OCH2), 3.37 (d, 3H, equat.
ArCHAr, 2J(HH) = 13), 3.32 (d, 1H, equat. ArCHAr, 2J(HH) =
3
13), 3.25 (s, 3H, OCH3), 1.70 (d, 1H, NHCHMePh, J = 7.0
Hz), 1.34 (s, 18H, C(CH3)), 0.96 and 0.94 (2s, 18H, C(CH3)),
OH signals not identified. 13C-{1H} NMR (CDCl3): δ 167.93
(C᎐O), 150.28–125.22 (arom. C), 75.55 (s, OCH ), 74.29 (s,
OCH2), 70.86 (s, OCH2CO), 58.87 (s, OCH3), 48.87 (s, CONH-
CHCH3Ph), 33.96 (C(CH3)), 31.78 and 31.01 (2s, C(CH3)),
31.40 and 31.25 (2s, ArCH2Ar) and 22.85 (s, CONHCH-
CH3Ph). Found: C, 78.71; H, 8.42; N, 1.59. Calc. for C57H73-
NO6: C, 78.86; H, 8.48; N, 1.61%.
5,11,17,23-Tetra-tert-butyl-25,27-bis(diphenylphosphinoyl-
methoxy)-26,28-bis{(1R,2S,5R)-menthyloxycarbonylmethoxy}-
calix[4]arene L6b. A solution of L6a (7.842 g, 7.53 mmol) in dry
THF–DMF (9 : 1, v/v) (250 cm3) was refluxed with ButONa
(1.664 g, 17.30 mmol) for 1 h. Then Ph2P(O)CH2OTs (6.400 g,
16.56 mmol) was added and the mixture refluxed for 3 d. After
cooling and filtration, the solvents were removed under reduced
pressure. The residue was taken up in CH2Cl2 (200 cm3) and
washed with a saturated NH4Cl–water solution (150 cm3)
and then with water (100 cm3). The organic layer was dried
over MgSO4, filtered and concentrated to ca. 15 cm3. Addition
of acetone with stirring and cooling gave a white precipitate
᎐
2
(R)-5,11,17,23-Tetra-tert-butyl-25,27-bis[(diphenyl-
phosphinoyl)methoxy]-26-(3-oxabutyloxy)-28-[(1-phenylethyl)-
carbamoylmethoxy]calix[4]arene L5c. A solution of L5b (6.000
g, 6.9 mmol) in toluene (150 cm3) was heated at 40 ЊC for 1 h in
the presence of NaH (0.415 g, 17.30 mmol). Ph2P(O)CH2OTs
(5.601 g, 14.50 mmol) was then added and the mixture stirred
for 3 d at 80 ЊC. The solvent was removed under reduced pres-
sure, and the residue taken up with CH2Cl2 (200 cm3). After
washing with saturated NH4Cl–water (3 × 200 cm3), then with
brine (200 cm3), the organic layer was dried over MgSO4. After
filtration, the solvent was removed in vacuo and addition of
MeOH afforded the product as a white solid. Yield: 8.5 g, 90%.
(Rf = 0.44 CH2Cl2–MeOH 94 : 6, v/v). Yield: 6.120 g, 55%. mp
1
264–270 ЊC. IR (KBr, cmϪ1): ν(C᎐O) 1749s, ν(P=O) 1205s. H
᎐
NMR (CDCl3): δ 7.88–7.65 and 7.46–7.24 (m, 20H, P(O)Ph2),
6.59–6.50 (m, 8H, m-H), 5.55 (m, 4H, OCH2P(O)Ph2), 4.79–
4.45 (m, 10H, OCH of Ment, OCH2CO2Ment and ArCH2Ar),
3.01–2.87 (m, 4H, ArCH2Ar), 1.96–0.63 (36H, Ment), 1.07
(s, 18H, But) and 0.95 (s, 18H, But). 13C-{1H} NMR (CDCl3):
δ 170.16 (s, C᎐O), 152.83–124.62 (arom. C), 74.17 (s, OCH of
᎐
OMent), 71.19 (s, OCH2CO2Ment), 70.68 (d, OCH2P(O)Ph2,
J(PC) = 74.8 Hz), 46.70, 27.96 and 25.91 (3s, CH of Ment),
40.70, 34.17 and 23.29 (3s, CH2 of Ment), 33.68 and 33.57 (2s,
C(CH3)3), 32.33 and 31.94 (2s, ArCH2Ar), 31.35 and 31.16 (2s,
C(CH3)3), 22.00, 20.70 and 16.16 (3s, CH3 of Ment). 31P-{1H}
NMR (CDCl3): δ 24.89 (s, P(O)Ph2). Found: C, 76.80; H, 8.42.
Calc. for C94H118O10P2: C, 76.81; H, 8.09%.
mp 162–164 ЊC. IR (KBr, cmϪ1): ν(C᎐O) 1684s. 1H NMR
᎐
3
(CDCl3): δ 9.38 (d, 1H, NH, J = 8.2), 7.87–7.21 (25H, arom.
H), 6.78 (s, 2H, m-H), 6.67 and 6.66 (AB spin system, 2H,
4
m-H, J(AB) = 1), 6.52 and 6.41 (AB spin system, 2H, m-H,
4J(AB) = 2), 6.47 (s, 2H, m-H), 5.19 (dq, AMX3 spin system, 4H,
NHCHMePh, 3J(AM) ≈ 3J(AX) = 7.0), 5.07 (s, 2H, PCH2),
4.98 (s, 2H, PCH2), 4.83 and 4.61 (AB spin system, 2H, OCH2-
C(O), 2J(AB) = 13.7), 4.66 and 3.04 (AB spin system, 2H,
5,11,17,23-Tetra-tert-butyl-25,27-bis(diphenylphosphino-
methoxy)-26,28-bis{(1R,2S,5R)-menthyloxycarbonylmethoxy}-
calix[4]arene L6. A mixture of the bis(phosphine oxide) L6b
(4.500 g, 3.06 mmol) and phenylsilane (6.665 g, ca. 7.6 cm3, 61.6
mmol) in toluene (40 cm3) was refluxed for 2 days. After cool-
ing, the solution was filtered and the solvent removed in vacuo.
The residue was dissolved in CH2Cl2 (ca. 5 cm3). Addition of
EtOH (40 cm3) with stirring and cooling afforded the product
as a white precipitate. Yield: 3.95 g, 90%. mp 164–169 ЊC. IR
(KBr, cmϪ1): ν(C᎐O) 1753s. 1H NMR (CDCl ): δ 7.52–7.40 and
2
ArCH2, J(AB) = 13.1), 4.55 and 2.79 (AB spin system, 2H,
ArCH2, 2J(AB) = 13.1), 4.45 and 2.98 (AB spin system,
2
2H, ArCH2, J(AB) = 12.8), 4.43 and 2.98 (AB spin system,
2H, ArCH2, 2J(AB) = 12.8), 3.73 (m, 2H, OCH2), 3.40 (m, 2H,
OCH2), 2.96 (s, 3H, OCH3), 1.56 (d, 1H, NHCHMePh, 2J = 7.0
Hz), 1.13 (s, 9H, C(CH3)3), 1.08 (s, 9H, C(CH3)3) and 0.95
(s, 18H, C(CH3)). 13C-{1H} NMR (CDCl ): δ 168.91 (C᎐O),
᎐
3
153.65–124.99 (arom. C), 72.96 (s, OCH2), 72.47 (s, OCH2),
71.92 (s, OCH2), 71.53 (s, OCH2), 71.26 (s, OCH2CO), 57.91 (s,
OCH3), 48.37 (NHCH), 33.75, 33.67 and 33.60 (3s, C(CH3)),
᎐
3
7.36–7.28 (m, 20H, PPh2), 6.88 and 6.85 (AB spin system, 4H,
J. Chem. Soc., Dalton Trans., 2001, 881–892
887

View Article Online
m-H, 4J = 2.4), 6.53 and 6.50 (AB spin system, 4H, m-H,
4J = 2.4), 5.15 and 4.94 (ABX spin system, 4H, OCHAHBPPh2,
J(AX) ≈ J(BX) = 3.1 Hz), 4.84–4.44 (m, 10H, OCH of Ment,
OCH2CO2Ment and ArCH2Ar), 3.10–2.98 (m, 4H, ArCH2Ar),
2.06–0.66 (36H, Ment), 1.17 (s, 18H, But) and 0.94 (s, 18H,
But). 13C-{1H} NMR (CDCl ): δ 170.02 (s, C᎐O), 153.51–
124.653 (arom. C), 76.79 (d, OCH2PPh2, J(PC) = 6.5 Hz), 74.14
(s, OCH of CO2Ment), 70.75 (s, OCH2CO2Ment), 46.93, 28.10
and 25.89 (3s, CH of CO2Ment), 40.97, 34.32 and 23.26 (3s,
CH2 of Ment), 33.83 and 33.68 (2s, C(CH3)3), 32.32 (br s,
ArCH2Ar), 31.49 and 31.26 (2s, C(CH3)3), 22.10, 20.98 and
16.21 (3s, CH3 of Ment). 31P-{1H} NMR (CDCl3): δ Ϫ21.40 (s,
PPh2). Found: C, 78.36; H, 8.46. Calc. for C94H118O8P2: C,
78.52; H, 8.27%.
(0.025 g, 0.126 mmol) in THF (1 cm3) was added to a solution
of [RhCl(nbd)]2 (0.029 g, 0.064 mmol) in CH2Cl2 (3 cm3). Stir-
ring was stopped after 5 min and the solution decanted to elim-
inate AgCl. The supernatant was filtered through Celite and
added to a solution of L1 (0.150 g, 0.126 mmol) in CH2Cl2 (30
cm3). After stirring for 12 h the solution was concentrated to
ca. 5 cm3. Addition of pentane afforded an orange precipitate.
᎐
3
1
Yield: 0.136 g, 74%. mp 196–198 ЊC (slow decomp.). H NMR
(CDCl3): δ 7.67–7.52 (20H, PPh2), 7.10 and 6.40 (2s, 8H, m-H),
4.41 (s br, 4H, HC᎐CH of nbd), 4.26 and 3.12 (AB spin system,
᎐
2
8H, ArCH2Ar, J = 12.8 Hz), 4.00 (m, 8H, OCH2), 3.96 (s br,
2H, CH of nbd), 3.75 (m, 4H, OCH2), 3.56 (m, 4H, OCH2),
3.48 (s, 6H, OCH3), 1.54 (s br, 2H, CH2 of nbd), 1.32 (s, 18H,
C(CH3)) and 0.79 (s, 18H, C(CH3)). 13C-{1H} NMR (CDCl3):
δ 153.00–124.81 (arom. C), 72.98, 71.39 and 68.10 (3 peaks,
OCH2), 58.12 (s, OCH3), 34.09 and 33.72 (2s, C(CH3)), 31.64
and 31.22 (2s, C(CH3)), 31.08 (s, ArCH2Ar) and 29.5 (PCH2,
tentative assignment). 31P-{1H} NMR (CDCl3) δ 16.33 (d, PPh2,
J(PRh) = 153 Hz). FAB mass spectrum: m/z (%): 1383.6 (56)
[(M Ϫ BF4)ϩ, expected isotopic profile]. Found: C, 64.30; H,
6.67. Calc. for C85H102BF4O6P2Rhؒ0.75CH2Cl2: C, 64.32; H,
6.56%.
5,11,17,23-Tetra-tert-butyl-25,27-bis(diphenylphosphinooxy)-
26,28-bis(3-oxabutyloxy)calix[4]arene L7. A solution of n-BuLi
(1.51 M in hexane, 3.5 cm3, 5.2 mmol) was slowly added to a
stirred solution of L1a (2.000 g, 2.614 mmol) in THF (100 cm3)
at Ϫ78 ЊC. After stirring for 30 min, a precooled solution (ca.
Ϫ40 ЊC) of Ph2PCl (1.147 g, 5.228 mmol) in THF (30 cm3) was
added dropwise. The mixture was maintained at Ϫ78 ЊC for 1 h,
then warmed to room temperature. The solvent was removed
in vacuo and the residue taken up with toluene (50 cm3); the
resulting suspension was filtered through Celite to remove LiCl.
The filtrate and the toluene washings were combined before
concentration to ca. 10 cm3. Addition of pentane afforded a
white product which was recrystallised from dichloromethane–
pentane. Yield: 2.200 g, 75%. mp 220–225 ЊC. 1H NMR
(CDCl3): δ 7.71–7.66 and 7.45–7.42 (2 sets of signals, 20H,
PPh2), 7.00 (s, 4H, m-H), 6.32 (s, 4H, m-H), 4.15 (t, 4H, OCH2,
3J = 5), 4.14 and 2.78 (AB spin system, 8H, ArCH2Ar,
2J(AB) = 13.0), 3.67 (t, 4H, OCH2, 3J = 5 Hz), 3.11 (s, 6H,
OCH3), 1.31 (s, 18H, C(CH3)) and 0.81 (s, 18H, C(CH3)).
13C-{1H} NMR (CDCl3): δ 153.50–124.67 (arom. C), 71.56 and
70.94 (s, OCH2), 58.61 (s, OCH3), 34.06 and 33.63 (2s, C(CH3)),
31.75 and 31.16 (2s, C(CH3)), ArCH2 signals are probably over-
lapping with C(CH3) signals. 31P-{1H} NMR (CDCl3): δ 122.6
(s, PPh2). Found: C, 77.40; H, 7.56. Calc. for C74H86O6P2ؒ
0.25CH2Cl2: C, 77.24; H, 7.55%.
(Norbornadiene){cis-P,PЈ-[5,11,17,23-tetra-tert-butyl-25,27-
bis(diphenylphosphinomethoxy)-26,28-bis(3-oxabutyloxy)calix-
[4]arene]}rhodium(I) tetrafluoroborate 3. A solution of AgBF4
(0.033 g, 0.172 mmol) in THF (1 cm3) was added to a solution
of [Rh(Cl)(nbd)]2 (0.039 g, 0.086 mmol) in CH2Cl2 (3 cm3). Stir-
ring was stopped after 5 min and the solution decanted to elim-
inate AgCl. The supernatant was filtered through Celite and
added to a solution of L2 (0.150 g, 0.129 mmol) in CH2Cl2 (30
cm3). After 12 h the solution was concentrated to ca. 5 cm3 and
addition of pentane afforded a white precipitate. Yield: 0.195 g,
79%. mp 198–199 ЊC (decomp.). 1H NMR (CDCl3): δ 8.01–7.60
(20H, PPh2), 6.96 and 6.48 (2s, 4H, m-H), 5.60 (s br, 4H,
OCH P), 4.18 (s br, 4H, HC᎐CH of nbd), 4.07 and 2.88 (AB
᎐
2
spin system, 4H, ArCH2CH2, 2J = 13.4 Hz), 3.94 (s br, 2H, CH
of nbd), 3.42 (s br, 4H, OCH2), 3.40 (s, 6H, OCH3), 3.22 (s br,
4H, OCH2), 1.55 (s, 2H, CH2 of nbd), 1.28 (s, 18H, C(CH3))
and 0.79 (s, 18H, C(CH3)). 13C-{1H} NMR (CDCl3): δ 154.12–
124.72 (arom. C), 82.05 (s, HC᎐CH of nbd), 73.75 (s, OCH ),
᎐
2
25,27-Bis(diethoxyphosphinooxy)-26,28-(3,6,9-trioxaundec-
ane-1,11-dioxy)calix[4]arene L9. A solution of n-BuLi (1.60 M
in hexane, 1.1 cm3, 1.76 mmol) was slowly added to a solution
of 25,27-dihydroxy-26,28-(3,6,9-trioxaundecane-1,11-dioxy)-
calix[4]arene (0.500 g, 0.86 mmol) in THF (100 cm3) at Ϫ78 ЊC.
After 0.5 h neat (EtO)2PCl (0.26 cm3, 1.80 mmol) was added
dropwise within 1 h to the orange solution maintained at
Ϫ78 ЊC. After stirring for 0.5 h at room temperature the solvent
was evaporated to dryness and the residue dissolved in pentane.
After storage at Ϫ20 ЊC for 1 h the suspension formed was
filtered through a glass frit. The solution was evaporated to
dryness yielding L9 as a colourless powder. Yield: 0.551 g, 78%.
71.73 (OCH2P, tent. assign.), 69.60 (s, OCH2), 69.50 (CH2 of
nbd), 58.76 (s, OCH3), 52.29 (s, CH of nbd), 33.84 and 33.62
(2s, C(CH3)), 31.49 and 30.97 (2s, C(CH3)) and 29.54 (s,
ArCH2). 31P-{1H} NMR (CDCl3): δ 23.7 (d, PPh2, J(PRh) = 152
Hz). FAB mass spectrum: m/z (%) 1355.7 (30) [(M Ϫ BF4)ϩ,
expected isotopic profile]. Found: C, 66.28; H, 6.68. Calc. for
C83H98BF4O6P2RhؒCH2Cl2: C, 66.02; H, 6.60%.
(ꢀ3-2-Methylallyl)-{P,PЈ-[5,11,17,23-tetra-tert-butyl-25,27-
bis(2-diphenylphosphinoethoxy)-26,28-bis(3-oxabutyloxy)-
calix[4]arene]}palladium(II) tetrafluoroborate 4. A solution of
AgBF4 (0.025 g, 0.128 mmol) in THF (1 cm3) was added to a
solution of [Pd(η3-C3H4Me)Cl]2 (0.029 g, 0.063 mmol) in
CH2Cl2 (3 cm3). Stirring was stopped after 5 min and the solu-
tion decanted to eliminate AgCl. The supernatant was filtered
through Celite and added to a solution of L1 (0.150 g, 0.126
mmol) in CH2Cl2 (30 cm3). After 12 h the solution was concen-
trated to ca. 5 cm3 and addition of pentane afforded a white
precipitate. Yield: 0.123 g, 70%. mp 182–184 ЊC (slow decomp.).
1H NMR (CDCl3): δ 7.63–7.51 (20H, PPh2), 7.11 and 6.41 (2s,
8H, m-H), 4.26 and 3.12 (AB spin system, 8H, ArCH2Ar,
2J = 12.7 Hz), 4.17 (m, 4H), 3.80 (m, 2H), 3.77 (m, 2H), 3.75
(m, 4H), 3.46 (m, 4H), 3.39 (s, 6H, OCH3), 3.23 (m, 2H), 1.75
(s, 3H, CH3C3H4), 1.32 (s, 18H, C(CH3)) and 0.79 (s, 18H,
C(CH3)). 13C-{1H} NMR (CDCl3): δ 154.16–124.58 (arom. C
and Cquat of allyl), 73.42 (d, PCH2CH2, 2J(PC) = 7), 70.70, 70.41
and 69.34 (3s, OCH2 and CH2 of allyl), 58.54 (s, OCH3), 34.06
and 33.47 (2s, C(CH3)), 31.56 and 30.94 (2s, C(CH3)), 30.83
(s, ArCH2), 29.39 (m, PCH2, J(PC) = 22 Hz) and 23.15
1
mp 220–221 ЊC. H NMR (CDCl3): δ 7.16 and 6.98 (AB2 spin
3
system, J = 8, t(2H) ϩ d(4H), m- and p-H of calix), 6.23 and
3
6.06 (AB2 spin system, J = 8, t(2H) ϩ d(4H), m- and p-H of
calix), 4.47 and 3.21 (AB quartet, 2J = 14, 4H each, ArCH2Ar),
4.30–4.00 (m, 16H, CH2 of crown-5 ϩ POCH2CH3), 3.77 (s,
8H, ArOCH2CH2OCH2CH2) and 1.31 (t, 12H, POCH2CH3).
13C-{1H} NMR (CDCl3): δ 154.68 (quat. aryl C-O), 147.10 (d,
2J(PC) = 6 Hz, quat. aryl C-O), 135.13 and 133.16 (2s, quat. aryl
C), 129.88, 128.28, 124.97 and 124.06 (4s, aryl CH), 74.10,
72.36 and 71.43 (3s, CH2 of crown-5), 61.42 (s, POCH2CH3),
31.89 (s, ArCH2) and 16.43 (s, POCH2CH3). 31P-{1H} NMR
(CDCl3): δ 140.0 (s). Found: C, 64.33; H, 6.62. Calc. for C44H56-
O11P2: C, 64.22; H, 6.86%.
(Norbornadiene){cis-P,PЈ-[5,11,17,23-tetra-tert-butyl-25,27-
bis(2-diphenylphosphinoethoxy)-26,28-bis(3-oxabutyloxy)calix-
[4]arene]}rhodium(I) tetrafluoroborate 2. A solution of AgBF4
888
J. Chem. Soc., Dalton Trans., 2001, 881–892

View Article Online
(CH3C3H4). 31P-{1H} NMR (CDCl3): δ 12.3 (s, PPh2). FAB mass
spectrum: m/z (%) 1349.6 (100) [(M Ϫ BF4)ϩ, expected isotopic
profile]. Found: C, 67.69; H, 7.14. Calc. for C82H101BF4O6P2Pd:
C, 67.71; H, 7.01%.
expected isotopic profile]. Found: C, 67.95; H, 6.96; N, 1.73.
Calc. for C86H107BF4N2O6P2Pd: C, 67.96; H, 7.1; N, 1.84%.
(R,R)-(ꢀ3-2-Methylallyl)-{P,PЈ-[5,11,17,23-tetra-tert-butyl-
25,27-bis(diphenylphosphinomethoxy)-26,28-bis[(1-phenylethyl)-
(ꢀ3-2-Methylallyl)-{P,PЈ-[5,11,17,23-tetra-tert-butyl-25,27-
bis(diphenylphosphinomethoxy)-26,28-bis(3-oxabutyloxy)calix-
[4]arene]}palladium(II) tetrafluoroborate 5. A solution of AgBF4
(0.025 g, 0.128 mmol) in THF (1 cm3) was added to a solution
of [Pd(η3-C3H4Me)Cl]2 (0.029 g, 0.073 mmol) in CH2Cl2
(3 cm3). Stirring was stopped after 5 min and the solution
decanted to eliminate AgCl. The supernatant was filtered
through Celite and added to a solution of L2 (0.150 g, 0.129
mmol) in CH2Cl2 (30 cm3). After 12 h the solution was concen-
trated to ca. 5 cm3 and addition of pentane afforded a white
carbamoylmethoxy]calix[4]arene]}palladium(II)
tetrafluoro-
borate 7. A solution of AgBF4 (0.029 g, 0.146 mmol) in THF (1
cm3) was added to a solution of [Pd(η3-C3H4Me)Cl]2 (0.029 g,
0.073 mmol) in CH2Cl2 (3 cm3). Stirring was stopped after
5 min and the solution decanted to eliminate AgCl. The super-
natant was filtered through Celite and added to a solution of
L4 (0.200 g, 0.110 mmol) in CH2Cl2 (30 cm3). After 12 h the
solution was concentrated to ca. 5 cm3 and addition of pen-
tane afforded a dark brown precipitate. Yield: 0.193 g, 93%.
mp 185–187 ЊC (slow decomp.). IR (KBr, cmϪ1): ν(N–H) 3340,
1
precipitate. Yield: 0.130 g, 72%. mp 200–205 ЊC (decomp.). H
ν(C᎐O) 1683, ν(B-F) 1057. 1H NMR (CDCl3): δ 7.64–7.21
᎐
NMR (CDCl3): δ 7.82–7.52 (20H, PPh2), 6.97 and 6.96
(AB spin system, 4H, m-H, J(AB) = 3), 6.48 and 6.45 (2s,
4H, m-H), 5.85 and 5.74 (AB spin system, 4H, OCH2P,
J(AB) = 12.9), 4.13 and 2.94 (AB spin system, 4H, ArCH2Ar,
2J = 12.9), 4.07 and 2.90 (AB spin system, 4H, ArCH2Ar,
2J = 13.5 Hz), 3.81 (s br, 2H, CH of allyl), 3.61 and 3.49 (2
broad signals, 2 × 2H, CH3OCH2), 3.29 and 3.27 (2s, 6H,
OCH3), 3.26 (m, 2H, CH of allyl), 3.15 (m, 4H, CH3OCH2-
CH2), 1.56 (s, 3H, CH3C3H4), 1.29 (s, 18H, C(CH3)), 0.79 (s, 9H,
C(CH3)) and 0.78 (s, 9H, C(CH3)). 13C-{1H} NMR (CDCl3):
δ 152.51–124.69 (arom. C and Cquat of allyl), 73.75 (s,
CH2CH2OCH3), 72.54 (t, OCH2P, tent. assignment, |J(PC) ϩ
3J(PЈC)| = 30 Hz), 69.93 and 69.56 (2s, CH3OCH2CH2),
58.65 and 58.57 (2s, OCH3), 33.89 and 33.62 (2s, C(CH3)),
31.49 and 30.97 (2s, C(CH3)), 29.87 and 29.73 (2s, ArCH2),
22.82 (CH3C3H4), CH2 of allyl not identified. 31P-{1H}
NMR (CDCl3): δ 18.3 (s, PPh2). FAB mass spectrum: m/z
(%) 1321.6 (100) [(M Ϫ BF4)ϩ, expected isotopic profile].
Found: C, 68.03; H, 6.89. Calc. for C80H97BF4O6P2Pd: C, 68.16;
H, 6.94%.
(m, 30H, PPh2), 6.91 (d, 1H, NH, 3J = 7), 6.89–6.23 (8H,
m-H), 6.38 (d, 1H, NH, 3J = 7 Hz), 6.05 and 5.80 (ABX
spin system with X = P, 4H, OCHAHBPPh2, J(AB) = 13,
J(AX) = 13, J(BX) = 20), 5.03 and 5.02 (2 quint, AMX3 spin
system, 2H, NHCHMePh, 3J(AM) ≈ 3J(AX) = 7), 4.32 (AB
2
spin system, 4H, OCH2CONHR, J(AB) = 15), 4.05–3.68 and
3.05–2.59 (two complex m, 12H, 4 overlapping ArCHAHBAr
signals and CH2 of allyl), 1.47 and 1.40 (2d, 6H, NHCH-
CH3Ph, 3J = 7.0 Hz), 1.34 (s, 3H, C3H4Me), 1.28 (s, 18H,
C(CH3)), 0.78 (s, 9H, C(CH3)) and 0.72 (s, 9H, C(CH3)). 13C-
{1H} NMR (CDCl ): δ 168.10 (s, C᎐O), 167.99 (s, C᎐O),
᎐
᎐
3
153.84–124.80 (arom. C and Cquat allyl), 73.83 and 73.53 (2s,
OCH2CONHR), 73.06 (t, OCH2P, |J(PC) ϩ 3J(PЈC)| = 37 Hz),
49.39 and 49.06 (2s, NHCHMePh), 33.85, 33.53 and 33.51
(3s, C(CH3)), 31.49 and 30.90 (2s, C(CH3)), 30.28 and 29.95
(2s, ArCH2Ar), 22.38 (s), 22.23 (s) (CH3C3H4). 31P-{1H} NMR
2
(CDCl3): δ 16.7 and 16.1 (AB spin system, PPh2, J(AB) = 43
Hz). FAB mass spectrum: m/z (%) 1527.1 (100) [(M Ϫ BF4)ϩ,
expected isotopic profile] and 1473.1 (20) [(M Ϫ BF4 Ϫ
C3H4Me)ϩ, expected isotopic profile]. Found: C, 69.61; H, 6.81;
N, 1.68. Calc. for C94H107BF4N2O6P2Pd: C, 69.86; H, 6.67; N,
1.73%.
(ꢀ3-2-Methylallyl){P,PЈ-[5,11,17,23-tetra-tert-butyl-25,27-
bis(diethylcarbamoylmethoxy)-26,28-bis(diphenylphosphino-
methoxy)calix[4]arene]}palladium(II) tetrafluoroborate 6.
A
(R)-(ꢀ3-2-Methylallyl)-{P,PЈ-[5,11,17,23-tetra-tert-butyl-
25,27-bis[diphenylphosphinomethoxy]-26-(3-oxabutyloxy)-
28-[(1-phenylethyl)carbamoylmethoxy]calix[4]arene]}pallad-
ium(II) tetrafluoroborate 8. A solution of AgBF4 (0.023 g, 0.118
mmol) in THF (1 cm3) was added to a solution of [Pd(η3-
C4H7)Cl]2 (0.023 g, 0.059 mmol) in CH2Cl2 (3 cm3). Stirring was
stopped after 5 min and the solution decanted to eliminate
AgCl. The supernatant was filtered through Celite and added to
a solution of L5 (0.150 g, 0.119 mmol) in CH2Cl2 (30 cm3). After
12 h the solution was concentrated to ca. 5 cm3 and addition
of pentane afforded a white precipitate. Yield: 0.130 g, 72%.
mp >280 ЊC. IR (KBr, cmϪ1): 1676s. The NMR spectra show
that two isomers are present. Below are given only the 1H NMR
solution of AgBF4 (0.023 g, 0.118 mmol) in THF (1 cm3) was
added to a solution of [Pd(η3-C3H4Me)Cl]2 (0.023 g, 0.059
mmol) in CH2Cl2 (3 cm3). Stirring was stopped after 5 min and
the solution decanted to eliminate AgCl. The supernatant was
filtered through Celite and added to a solution of L3 (0.150 g,
0.118 mmol) in CH2Cl2 (30 cm3). After 12 h the solution was
concentrated to ca. 5 cm3 and addition of pentane afforded a
dark brown precipitate. Yield: 0.120 g, 67%. mp 181–183 ЊC
(slow decomp.). IR (KBr, cmϪ1): ν(C᎐O) 1653, ν(B-F) 1060. 1H
᎐
NMR (CDCl3): δ 7.85–7.76 and 7.57–7.30 (m, 20H, PPh2), 7.02
and 6.80 (AB spin system, 4H, m-H, J(AB) = 2), 6.59 (ABXXЈ
spin system with X,XЈ = P, 4H, OCH2PPh2, 2J(AB) = 9,
|J(AX) ϩ J(AXЈ)| = 4, J(BX) = not determined), 6.46 (s, 2H,
m-H), 6.20 (s, 2H, m-H), 4.38 and 3.18 (AB spin system, 4H,
1
data of the major compound. H NMR (CDCl3): δ 7.83–7.17
(arom. H ϩ NH), 7.02 (s, 2H, m-H), 6.80 and 6.75 (AB spin
system, 2H, m-H, J(AB) ≈ 3), 6.60 and 6.55 (AB spin system,
2H, m-H, J(AB) ≈ 2.5), 6.27 and 6.18 (AB spin system, 2H,
m-H, J(AB) ≈ 3), 6.11 and 5.50 (two m, 4H, PCH2), 4.95 (dq,
2
ArCH2Ar, J = 13.4), 4.07 and 4.02 (2s, 4H, OCH2CONEt2),
3.70 (s br, 2H, CHsyn of allyl), 3.63 and 2.49 (AB spin system,
2
2H, ArCH2Ar, J = 13.1), 3.52–3.42 (3q, 6H, NCH2CH3), 3.15
3
3
(s br, 2H, CHanti of allyl), 3.03 (q, 2H, NCH2CH3, J = 7.0),
AMX3 spin system, 1H, NHCHMePh, J(AM) ≈ 3J(AX) = 7),
1.30 (s, 18H, But), 1.23–1.17 (3t, 9H, NCH2CH3), 1.15 (t, 3H,
4.45 (AB spin system, 2H, OCH2C(O), tent. assign.), 3.80 (2d,
2H, axial ArCHAr), 3.60 (2d, 2H, axial ArCHAr), 3.65–3.10
(several m, not assigned), 3.20 (s, 3H, OCH3), 2.75 (d, 2H,
equat. ArCHAr, J(HaxHeq) = 13), 2.55 (d, 2H, equat. ArCHAr,
3
NCH2CH3, J = 7.0 Hz), 0.91 (s, 3H, CH3C3H4), 0.83 (s, 9H,
But) and 0.70 (s, 9H, But). 13C-{1H} NMR (CDCl3): δ 166.77
and 166.55 (2s, C᎐O), 153.95–107.79 (arom. C and Cquat-allyl),
᎐
73.24 (t, OCH2PPh2, |J(PC) ϩ 3J(PЈC)| = 30 Hz), 72.62 and
72.47 (2s, OCH2CONEt2), 40.94, 40.46 and 39.95 (3s,
NCH2CH3), 33.84, 33.66 and 33.47 (3s, C(CH3)3), 31.50 and
30.94 (2s, C(CH3)3), 31.30 and 29.21 (s, ArCH2Ar), 21.68 (s,
CH3C3H4), 14.29, 14.07 and 13.08 (3s, NCH2CH3), CH2 of allyl
not detected. 31P-{1H} NMR (CDCl3): δ 14.7 (s, PPh2). FAB
mass spectrum: m/z (%) 1431.4 (100) [(M Ϫ BF4)ϩ, expected
isotopic profile] and 1377.3 (35) [(M Ϫ BF4 Ϫ C3H4Me)ϩ,
J(HaxHeq) = 13), 1.55 (d, 1H, NHCHMePh, J = 7 Hz), 1.30 (s,
2
18H, C(CH3)3), 0.80 (s, 9H, C(CH3)3) and 0.70 (s, 9H, C(CH3)3).
Signals of allyl CH2 and OCH2CH2O could not be assigned due
to overlapping. 31P NMR (CDCl3): δ 17.03 and 15.24 (AB spin
system, PPh2 (isomer 1), J(AB) = 38), 17.94 and 16.53 (AB spin
system, PPh2 (isomer 2), J(AB) = 39 Hz). FAB mass spectrum:
m/z (%) 1424.1 (100) [(M Ϫ BF4)ϩ, expected isotopic profile]
and 1370.0 (30) [(M Ϫ BF4 Ϫ C3H4Me)ϩ]. Found: C, 67.29; H,
J. Chem. Soc., Dalton Trans., 2001, 881–892
889

View Article Online
6.36; N, 0.87. Calc. for C87H102BF4NO6P2Pdؒ0.5CH2Cl2: C,
67.57; H, 6.67; N, 0.90%.
190–195 ЊC (slow decomp.). IR (KBr, cmϪ1): ν(C᎐O) 1758 and
᎐
1
1727, ν(B–F) 1062. H NMR (CDCl3): δ 8.21–8.07, 7.63–7.50
and 7.41–7.20 (20H, PPh2), 7.03 and 6.97 (AB spin system, 4H,
m-H, J(AB) = 3), 6.17 (s, 2H, m-H), 6.08 (s, 2H, m-H), 4.60 and
4.53 (2 dt, 2H, OCH of Ment, 3J = 10.7, 4), 4.20 (s, 2H, OCH2-
C(O)Ment), 4.03 and 2.94 (AB spin system, 2H, OCH2C-
(O)Ment, J(AB) = 16.8), 3.82 and 2.76 (AB spin system, 4H,
ArCH2Ar, 2J = 13.2), 3.76 and 2.53 (ABX spin system with
(ꢀ3-2-Methylallyl){P,PЈ-[5,11,17,23-tetra-tert-butyl-25,27-
bis(diphenylphosphinomethoxy)-26,28-bis{(1R,2S,5R)-menthyl-
oxycarbonylmethoxy}calix[4]arene]}palladium(II) tetrafluoro-
borate 9. A solution of AgBF4 (0.029 g, 0.146 mmol) in THF
(1 cm3) was added to a solution of [Pd(η3-C3H4Me)Cl]2 (0.029
g, 0.073 mmol) in CH2Cl2 (3 cm3). Stirring was stopped after
5 min and the solution decanted to eliminate AgCl. The super-
natant was filtered through Celite and added to a solution of L6
(0.210 g, 0.146 mmol) in CH2Cl2 (30 cm3). After 12 h the solu-
tion was concentrated to ca. 5 cm3 and addition of pentane
2
5
X = P, 2H, ArCH2Ar, J = 13.2, J(PH) = 4 Hz), 3.52, 3.50 and
3.42 (2H, 3 signals of Hsyn of allyl), 3.48 (pseudo t, 2H, CHanti
of allyl), 1.65–0.62 (several multiplets br, 36 H of Ment), 1.55
(s, 3H, CH3C3H4Me), 1.35 (s, 18H, But), 0.73 (s, 9H, But) and
0.66 (s, 9H, But). 13C-{1H} NMR (CDCl3): δ 168.49 and 168.36
afforded a yellow crystalline powder. Yield: 0.150 g, 60%.
(2s, C᎐O), 151.34–124.01 (arom. C), 75.05 and 74.68 (2s, OCH
᎐
1
mp >280 ЊC. IR (KBr, cmϪ1): ν(C᎐O) 1747, ν(B–F) 1057. H
of Ment), 71.39 and 71.37 (2s, OCH2CO2Ment), 46.78, 46.62,
26.14 (3s, CH of Ment), 40.89, 40.62, 34.13 and 23.50 (4s, CH2
of Ment), 34.19 (s, C(CH3)3), 32.50 and 32.13 (2s, ArCH2Ar),
31.60, 31.11 and 30.95 (3s, C(CH3)3), 22.22, 22.06, 20.74
and 16.35 (4s, CH3C3H4Me and CH3 of Ment). 31P-{1H}
NMR (CDCl3): δ 128.7 (s, PPh2). FAB mass spectrum: m/z
(%) 1569.6 (100) [(M Ϫ BF4)ϩ, expected isotopic profile] and
1514.6 (11) [(M Ϫ BF4 Ϫ C3H4Me)ϩ, expected isotopic profile].
Calc. for C96H121BF4O8P2Pd: C, 67.80; H, 6.78. Found: C,
67.62; H, 6.97%.
᎐
NMR (CDCl3): δ 7.75–7.67 and 7.61–7.35 (20H, PPh2), 7.00
and 6.87 (AB spin system, 4H, m-H, J(AB) ≈ 2), 6.45 (s, 2H,
m-H), 6.29 (s, 2H, m-H), 6.14 and 5.59 (m, A parts of two
overlapping AB spin systems, 2H, PCH2), 5.59 (m, B parts of
two overlapping AB spin systems, PCH2), 4.74 and 4.68 (2 dt,
2H, OCH of Ment, 3J ≈ 10, 3J ≈ 4 Hz), 4.35–3.27 (several
unresolved signals), 3.08 (d, 2H, ArCHAr), 2.72 (d, 1H,
ArCHAr), 2.65 (d, 1H, ArCHAr), 2.05–1.95 and 1.95–0.71
(several multiplets br, 36 H of Ment), 1.50 (s, 3H, CH3C3-
H4Me), 1.29 (s, 18H, But), 0.77 (s, 9H, But) and 0.72 (s, 9H,
But). 31P-{1H} NMR (CDCl3): δ 16.5 and 15.9 (AB spin system,
PPh2, J(PPЈ) = 38 Hz). FAB mass spectrum: m/z (%) 1597.4
(100) [(M Ϫ BF4)ϩ, expected isotopic profile]. Found: C, 69.63;
H, 7.30. Calc. for C98H125BF4O8P2Pd: C, 69.81; H, 7.47%.
Chloro(ꢀ6-p-cymene)[{P,PЈ-[5,11,17,23-tetra-tert-butyl-
25,27-bis-(diethylcarbamoylmethoxy)-26,28-bis(diphenylphosphin-
omethoxy)calix[4]arene]}ruthenium(II) tetrafluoroborate 12. A
solution of AgBF4 (0.023 g, 0.118 mmol) in THF (1 cm3) was
added to a stirred solution of [RuCl2(p-MeC6H4Pri)]2 (0.036 g,
0.059 mmol) in CH2Cl2 (5 cm3). Stirring was stopped after 5
min and the solution decanted in order to remove AgCl. The
supernatant and CH2Cl2 washings of the AgCl precipitate were
filtered through Celite into a solution of L3 (0.150 g, 0.118
mmol) in CH2Cl2 (30 cm3). After stirring for 3 h the solution
was concentrated to ca. 2 cm3. The yellow product was obtained
by slow recrystallisation from a CH2Cl2–Et2O–hexane mixture.
(ꢀ3-2-Methylallyl){P,PЈ-[5,11,17,23-tetra-tert-butyl-25,27-
bis(diphenylphosphinooxy)-26,28-bis(3-oxabutyloxy)calix[4]-
arene]}palladium(II) tetrafluoroborate 10. A solution of AgBF4
(0.026 g, 0.134 mmol) in THF (1 cm3) was added to a solution
of [Pd(η3-C3H4Me)Cl]2 (0.026 g, 0.066 mmol) in CH2Cl2
(3 cm3). Stirring was stopped after 5 min and the solution
was decanted to eliminate AgCl. The supernatant was filtered
through Celite and added to a solution of L7 (0.150 g, 0.132
mmol) in CH2Cl2 (30 cm3). After 12 h the solution was concen-
trated to ca. 5 cm3 and addition of pentane afforded a white
Yield: 0.050 g, 52%. mp 218–220 ЊC. IR (KBr, cmϪ1): ν(C᎐O)
᎐
1
1650s, ν(B–F) 1055s br. H NMR (CDCl3): δ 7.88–7.69 and
7.48–7.33 (m, 20H, PPh2), 6.93 and 6.90 (2 s br, 4H, m-H), 6.43
and 5.25 (ABXXЈ spin system with X = XЈ = P, 4H, OCH2PPh2,
2J(AB) = 13.4, J(AX) and J(BX) not determined), 6.27 and 6.23
(2s, 4H, m-H), 5.75 and 4.85 (AAЈBBЈ spin system, 8H, C6H4 of
p-cymene, 3J = 6.1), 4.43 and 3.05 (AB spin system, 8H,
1
precipitate. Yield: 0.90 g, 50%. mp 185–187 ЊC (decomp.). H
NMR (CDCl3): δ 8.28–8.01 and 7.67–7.62 (20H, PPh2), 7.00
(s broad, 4H, m-H), 6.17 and 6.07 (2s, 2 × 2H, m-H), 3.91
and 3.79 (2 m, 4H, OCH2), 3.72 and 2.61 (AB spin system,
2
2
4H, ArCH2Ar, J = 13.4), 3.41 and 2.45 (AB spin system, 4H,
ArCH2Ar, J = 14.3), 4.30 and 3.92 (2s, 4H, OCH2CONEt2),
ArCH2Ar, 2J = 13.3 Hz), 3.38 (s br, 2H, Hsyn of allyl), 3.11
(s, 3H, OCH3), 3.00 (m, 4H, OCH2), 2.93 (s, 3H, OCH3), 1.60
(s, 3H, CH3C3H4Me), 1.36 (s, 18H, C(CH3)), 0.76 (s, 9H,
C(CH3)) and 0.68 (s, 9H, C(CH3)). 13C-{1H} NMR (CDCl3):
δ 150.77–123.71 (arom. C and Cquat of allyl), 72.36 (s,
CH2CH2OCH3), 69.89 and 69.21 (2s, CH3OCH2), 58.61 and
58.09 (2s, OCH3), 34.22 and 33.66 (2s, C(CH3)), 32.09 (s,
ArCH2Ar), 31.63, 31.12 and 31.00 (3s, C(CH3)), 22.36
(CH3C3H4Me), CH2 of allyl not found. 31P-{1H} NMR
(CDCl3): δ 128.2 (s, PPh2). FAB mass spectrum: m/z (%) 1293.5
(100) [(M Ϫ BF4)ϩ, expected isotopic profile] and 1238.4 (15)
[M Ϫ BF4 Ϫ C3H4Me)ϩ, expected isotopic profile]. Found: C,
67.62; H, 6.97. Calc. for C78H93BF4O6P2Pd: C, 67.8; H, 6.78%.
3.77 and 2.62 (AB spin system, 8H, ArCH2Ar, J = 13.1), 3.41
2
(q, 4H, N(CH2CH3)2, 3J = 7.0), 3.15 (m, 4H, two N(CH2CH3)2),
2.57 (q, 4H, N(CH2CH3)2, 3J = 7.0), 2.42 (m, 2H, CH(CH3)2 of
p-cymene), 1.29 (s, 18H, But), 1.25 (s, 6H, ArCH3 of p-cymene),
1.21 (m, 12H, two NCH2CH3), 0.98 (t, 6H, NCH2CH3, 3J = 6.7
Hz), 0.94 (d, 12H, CH(CH3)2 of p-cymene), 0.75 (s, 9H, But)
and 0.73 (s, 9H, But). 13C-{1H} NMR (CDCl3): δ 168.14 and
166.49 (2s, C᎐O), 152.30–123.54 (arom. C of PPh and calix-
᎐
2
arene), 0.98 (s, Cquat of p-cymene), 72.77 and 70.09 (2s, OCH2-
CONEt2), 71.01 (m, OCH2PPh2, tentative assignment), 41.26,
41.06 and 40.28 (3s, NCH2CH3), 33.52 and 32.24 (2s, C(CH3)3),
31.35, 30.95 and 30.76 (3s, C(CH3)3), 31.69 (s, ArCH2Ar), 20.73
(s, (CH3)2CH of p-cymene), 14.81, 14.52, 14.15, 12.94 and 12.50
(5s, N(CH2CH3) and ArCH3 of p-cymene), Cquat, (CH3)2CH
and CH arom. of p-cymene not determined. 31P-{1H} NMR
(CDCl3): δ 26.4 (s, PPh2). FAB mass spectrum: m/z (%) 1541.6
(23) [(M Ϫ BF4)ϩ] and 1407.6 (100) [(M Ϫ BF4 Ϫ p-cymene)ϩ].
Found: C, 68.05; H, 6.87; N, 1.69. Calc. for C92H114BClF4-
N2O6P2Ru: C, 67.83; H, 7.05; N, 1.72%.
(ꢀ3-2-Methylallyl)-{P,PЈ-[5,11,17,23-tetra-tert-butyl-25,27-
bis(diphenylphosphinooxy)-26,28-bis{(1R,2S,5R)-menthyloxy
carbonylmethoxy}calix[4]arene]}palladium(II) tetrafluoroborate
11. A solution of AgBF4 (0.029 g, 0.146 mmol) in THF (1 cm3)
was added to a solution of [Pd(η3-C3H4Me)Cl]2 (0.029 g,
0.073 mmol) in CH2Cl2 (3 cm3). Stirring was stopped after 5
min and the solution decanted to eliminate AgCl. The super-
natant was filtered through Celite and added to a solution of L8
(0.210 g, 0.149 mmol) in CH2Cl2 (30 cm3). After 12 h the solu-
tion was concentrated to ca. 5 cm3 and addition of pentane
afforded a yellow crystalline powder. Yield: 0.150 g, 60%. mp
Chloro(ꢀ6-p-cymene){P,PЈ-[(R,R)-5,11,17,23-tetra-tert-butyl-
25,27-bis(diphenylphosphinomethoxy)-26,28-bis{(1-phenylethyl)-
carbamoylmethoxy}calix[4]arene]}ruthenium(II) tetrafluorobor-
ate 13. A solution of AgBF4 (0.021 g, 0.110 mmol) in THF
(1 cm3) was added to a stirred solution of [RuCl2(p-MeC6-
890
J. Chem. Soc., Dalton Trans., 2001, 881–892

View Article Online
H4Pri)]2 (0.034 g, 0.055 mmol) in CH2Cl2 (5 cm3). Stirring was
stopped after 5 min and the solution decanted in order to
remove AgCl. The supernatant and dichloromethane washings
of the AgCl precipitate were filtered through Celite into a solu-
tion of L4 (0.150 g, 0.110 mmol) in CH2Cl2 (30 cm3). After
stirring for 3 h, the solution was concentrated to ca. 2 cm3
and the product precipitated with Et2O. Recrystallisation from
CH2Cl2–Et2O–hexane afforded 13 as an analytically pure yel-
low powder. Yield: 0.175 g, 90%. mp 206–209 ЊC. IR (KBr,
CH2Cl2 (30 cm3) was added at 0 ЊC a solution of L4 (0.200 g,
0.146 mmol) in CH2Cl2 (20 cm3). After stirring for 24 h the
solution was evaporated to dryness and the residue taken up
with CHCl3. Addition of diethyl ether yielded complex 15 as an
orange powder. Yield: 0.150 g, 55%. mp 187–190 ЊC. IR (KBr,
cmϪ1): ν(NH) 3425 and 3330, ν(C᎐O) 1684s, 1669s and 1656s.
᎐
1H NMR (CDCl3): δ 8.05–7.83 and 7.80–7.12 (30H, arom. H),
4
6.89 and 6.83 (AB spin system, 4H, m-H, J ≈ 2), 6.09 (d, 2H,
3
4
NH, J = 8), 6.01 and 5.99 (AB spin system, 4H, m-H, J < 1),
5.46 (s br, 4H, OCH2PPh2), 5.15 and 5.10 (AB spin system, 4H,
arom. of p-cymene, 3J = 7), 5.04 (dq, 2H, NHCHMePh),
4.47 and 4.36 (AB spin system, 4H, OCH2CO, J(AB) = 16 Hz),
1
cmϪ1): ν(C᎐O) 1685 and 1653. H NMR (CDCl ): δ 7.77–7.66
᎐
3
and 7.53–7.17 (m, 32H, arom. H and NH), 6.92 and 6.75 (AB
spin system, 2H, m-H, 4J = 2.2), 6.87 (s, 2H, m-H), 6.56 (d, 2H,
NH, 3J = 8), 6.30 and 6.27 (AB spin system, 2H, m-H, 4J = 1.8),
2
4.25 and 2.72 (AB spin system, 4H, ArCH2Ar, J = 15.0), 4.14
and 2.61 (AB spin system, 4H, ArCH2Ar, J = 13.7), 2.60 (m,
4
2
6.21 and 6.11 (AB spin system, 2H, m-H, J = 2.2), 5.84 and
4.62 (ABX spin system with X = P, 2H, PCH2 tent. assign.,
J(AB) = 1, J(AX) = 17, J(BX) = 0), 5.79 and 5.75 (ABX spin
system, 2H, ArH of p-cymene (tent. assign.), J(AB) = 2), 5.62 (s
br, 2H, PCH2), 5.10 (dq, 1H, CHMe), 4.96 and 4.78 (AB spin
system, 2H, Ar H of p-cymene, 3J(AB) = 3), 4.43 and 4.16 (AB
spin system, 2H, OCH2CONH, J(AB) = 15), 3.79 and 3.64 (A
parts of 4 overlapping AB spin systems, 4H, ArCH2Ar), 3.58
(s, 2H, OCH2C(O)), 2.97 (d, B parts of AB spin systems, 1H,
ArCH2Ar, J(AB) = 15), 2.72–2.62 (B part of 3 overlapping AB
spin systems, 3H, ArCH2Ar), 2.55 (hept, 2H, CH(CH3)2 of p-
cymene), 1.58 (d, 3H, NCHCH3, 3J = 7), 1.37 (d, 3H,
2H, CH(CH3)2 of p-cymene), 1.85 (s, 6H, ArCH3 of p-cymene),
3
1.28 (d, 6H, NHCHCH3, J = 7.0), 1.26 (s, 18H, But), 0.98 (d,
3
6H, CH(CH3)2 of p-cymene, J = 7.0), 0.90 (d, 3H, CH(CH3)2
of p-cymene, 3J = 7.0 Hz) and 0.69 (s, 18H, But). 13C-{1H}
NMR (CDCl ): δ 169.19 (s, C᎐O), 154.58–124.41 (arom. C of
᎐
3
PPh2 and calix), 108.68 and 93.93 (2s, Cquat of p-cymene), 91.61,
90.07, 85.50 and 84.87 (4s, arom. CH of p-cymene), 72.11
(s, OCH2CO), 71.70 (d, OCH2PPh2, J(PC) = 21 Hz), 48.76
(s, NHCH(CH3)Ph), 33.97 and 33.40 (2s, C(CH3)3), 32.02 and
30.28 (s, ArCH2Ar), 31.64 and 31.02 (2s, C(CH3)3), 22.60
(s, CH3), 22.00 and 21.43 (3s, CH3) and 17.43 (s, ArCH3 of
p-cymene). 31P-{1H} NMR (CDCl3): δ 23.4 (s, PPh2). FAB mass
spectrum: m/z (%) 1981.5 (13) [Mϩ] and 1943.6 (50)
[(M Ϫ Cl)ϩ]. Found: C, 65.15; H, 6.08; N, 1.27. Calc. for
C102H128Cl4N2O6P2Ru2ؒCHCl3: C, 65.07; H, 6.35; N, 1.37%.
3
NCHCH3, J = 7), 1.29 (s, 9H, But), 1.28 (s, 9H, But), 1.17 (s,
3H, ArCH3 of p-cymene), 1.05 (d, 6H, CH(CH3)2 of p-cymene,
3J = 7), 1.01 (d, 6H, CH(CH3)2 of p-cymene, 3J = 7 Hz), 0.80 (s,
9H, But) and 0.71 (s, 9H, But). 31P-{1H} NMR (CDCl3): δ 26.9
and 25.37 (AB spin system, PPh2, J(AB) = 49 Hz). FAB mass
spectrum: m/z (%) 1981 (13) [Mϩ], 1637.7 (4) [(M Ϫ BF4)ϩ] and
1503.6 (3) [(M Ϫ BF4 Ϫ p-MeC6H4Pri)ϩ]. Found: C, 64.82; H,
6.92; N, 1.30. Calc. for C51H64Cl2NO3PRu: C, 65.03; H, 6.85;
N, 1.49%.
[25,27-Bis(diethoxyphosphinooxy)-26,28-(3,6,9-trioxaundec-
ane-1,11-dioxy)calix[4]arene]silver(I) tetrafluoroborate 16. To a
stirred solution of L9 (0.200 g, 0.24 mmol) in THF (10 cm3) was
added a solution of AgBF4 (0.047 g, 0.25 mmol) in THF (10
cm3). After 0.5 h, concentration to ca. 5 cm3 resulted in form-
ation of a white precipitate which was filtered off. Yield: 0.224
ꢁ-P,PЈ-[5,11,17,23-Tetra-tert-butyl-25,27-bis(diethylcarb-
amoylmethoxy)-26,28-bis(diphenylphosphinomethoxy)calix[4]-
arene]-bis[dichloro(p-cymene)ruthenium(II)] 14. To a solution
of [RuCl2(p-MeC6H4Pri)]2 (0.175 g, 0.280 mmol) in CH2Cl2
(30 cm3) was added at 0 ЊC a solution of L3 (0.360 g, 0.280
mmol) in CH2Cl2 (20 cm3). After stirring for 1 h the solution
was concentrated to ca. 5 cm3. Diethyl ether was added to yield
complex 14 as an analytically pure orange powder (0.300 g,
1
g, 92%. mp 220 ЊC (decomp.). H NMR (CDCl3): δ 7.15 and
3
6.96 (AB2 spin system, t(2H) ϩ d(4H), J = 8, m- and p-H of
3
calix), 6.70 and 6.53 (AB2 spin system, t(2H) ϩ d(4H), J = 8,
2
m- and p-H of calix), 4.77 and 3.28 (AB quartet, J = 14 Hz,
4H each, ArCH2), 4.30–3.80 (m, 24H, CH2 of crown-5 ϩ
POCH2CH3) and 1.38 (t, 12H, POCH2CH3). 13C-{1H} NMR
(CDCl3): δ 154.69 and 147.66 (2s, quat. aryl C-O), 135.14 and
133.16 (2s, quat. aryl C), 129.88, 128.29, 124.98 and 124.06 (4s,
aryl C-O), 74.11, 72.38, 71.52 and 71.40 (4s, CH2 of crown-5),
61.43 (s, POCH2CH3), 31.91 (s, ArCH2) and 16.42 (s, POCH2-
CH3). 31P-{1H} NMR (CDCl3): δ 105.9 (2d, J(P–Ag107) = 778,
J(P–Ag109) = 900 Hz). FAB mass spectrum: m/z (%) 931.2 (100)
[Mϩ]. Found: C, 52.11; H, 5.62. Calc. for C44H56AgBF4O11P2: C,
51.94; H, 5.55%.
60%). mp 224–226 ЊC. IR (KBr, cmϪ1): ν(C᎐O) 1646s. 1H NMR
᎐
(CDCl3): δ 8.13–8.05 and 7.40–7.27 (m, 20H, PPh2), 6.82 (s, 4H,
m-H), 6.07 (s, 4H, m-H), 5.72 (broad signal, 4H, OCH2PPh2),
5.21 and 5.15 (AAЈBBЈ spin system, 8H, C6H4 of p-cymene,
3J = 5.5), 4.46 (s, 4H, OCH2CONEt2), 4.11 and 2.52 (AB spin
2
system, 8H, ArCH2Ar, J = 13.1), 3.28 (q, 4H, N(CH2CH3)2,
3J = 7.0), 2.68 (q, 4H, N(CH2CH3)2, 3J = 7.0), 2.60 (m, 2H,
CH(CH3)2 of p-cymene), 1.90 (s, 6H, ArCH3 of p-cymene), 1.25
(s, 18H, But), 1.01 (d, 12H, CH(CH3)2 of p-cymene), 1.00 (t,
Hydroformylation reactions with complexes 2 and 3
3
6H, NCH2CH3, J = 7.0), 0.73 (s, 18H, But) and 0.67 (t, 6H,
The catalytic runs were performed in a 100 cm3 glass-lined steel
autoclave containing a magnetic stirring bar. In a typical
experiment, a solution of the complex (0.017 mmol) in
benzene–CH2Cl2 (14 : 3, v/v, 15 cm3) was introduced under
argon into the autoclave. The autoclave was pressurised (20 bar)
with CO–H2 (1 : 1) and heated at 40 ЊC for 2 h. After cooling and
depressurisation, styrene was introduced (870 equivalents for
2 and 600 for 3). The reaction was then carried out under
40 bar CO–H2 at 40 ЊC. The observed conversions were 80%
for 2 (after 100 h reaction time) and 95% for 3 (after 80 h). In
both experiments, 2-phenylpropanal and 3-phenylpropanal
were formed in a 95 : 5 ratio.
3
NCH2CH3, J = 7.0 Hz). 13C-{1H} NMR (CDCl3): δ 168.43 (s,
C᎐O), 155.09–124.44 (arom. C of PPh and calixarene), 108.82
᎐
2
and 93.75 (2s, arom. Cquat of p-cymene), 90.99 and 84.82 (2s,
arom. CH of p-cymene), 72.29 (d, OCH2PPh2, J(PC) = 22 Hz),
69.75 (s, OCH2CONEt2), 41.23 and 39.95 (2s, NCH2CH3),
33.92 and 33.41 (2s, C(CH3)3), 31.67 and 30.39 (2s, C(CH3)3),
31.49 (d, ArCH2Ar), 21.83 (s, (CH3)2CH of p-cymene), 17.38
(s, ArCH3 of p-cymene), 14.26 and 13.08 (2s, N(CH2CH3)2).
31P-{1H} NMR (CDCl3): δ 27.2 (s, PPh2). FAB mass spectrum:
m/z (%) 1678 (3) [(M Ϫ 2Cl Ϫ p-MeC6H4Pri)ϩ] and 1578 [(M Ϫ
2Cl Ϫ Ru Ϫ p-MeC6H4Pri)ϩ]. Found: C, 64.82; H, 6.92; N, 1.39.
Calc. for C51H64Cl2NO3PRu: C, 65.03; H, 6.85; N, 1.49%.
Palladium catalysed allylic alkylation
ꢁ-P,PЈ-[(R,R)-5,11,17,23-Tetra-tert-butyl-25,27-bis(diphenyl-
phosphinomethoxy)-26,28-bis{(1-phenylethyl)carbamoylmeth-
oxy}calix[4]arene]-bis[dichloro(p-cymene)ruthenium(II)] 15. To a
solution of [RuCl2(p-MeC6H4Pri)]2 (0.090 g, 0.146 mmol) in
A suspension of sodium malonate (2.4 mmol) was prepared at
25 ЊC from dimethyl malonate (0.29 mmol) in THF (5 cm3) and
NaH (0.100 g, 60% in mineral oil). A solution of 1,3-diphenyl-
J. Chem. Soc., Dalton Trans., 2001, 881–892
891

View Article Online
2-propenyl acetate (0.300 g, 1.2 mmol) in THF (1 cm3) and a
solution of the catalyst were then added to the malonate solu-
tion. The mixture was stirred under reflux until completion of
the reaction. The reaction was monitored by TLC (Rf = 0.5
(starting compound), 0.2 (alkylation product); SiO2; hexane–
ethyl acetate 5 : 1, v/v).
16 B. Xu and T. M. Swager, J. Am. Chem. Soc., 1993, 115, 1159.
17 P. J. A. Kenis, E. G. Kerver, B. H. M. Snellink-Ruël, G. J. van
Hummel, S. Harkema, M. C. Flipse, R. H. Woudenberg,
J. F. J. Engbersen and D. N. Reinhoudt, Eur. J. Org. Chem., 1998,
1089.
18 C. Wieser-Jeunesse, D. Matt, M. R. Yaftian, M. Burgard and
J. M. Harrowfield, C. R. Acad. Sci., Sér. IIc, 1998, 479.
19 C. Floriani, D. Jacoby, A. Chiesi-Villa and C. Guastini, Angew.
Chem., Int. Ed. Engl., 1989, 28, 1376.
20 D. V. Khasnis, J. M. Burton, J. D. McNeil, H. Zhang and
M. Lattman, Phosphorus, Sulfur Silicon Relat. Elem., 1993, 75,
253.
X-Ray crystallography
Crystals of complex 16 suitable for diffraction study were
obtained by slow diffusion of tetrahydrofuran into a dichloro-
methane solution of the compound.
21 C. Loeber, D. Matt, A. De Cian and J. Fischer, J. Organomet.
Chem., 1994, 475, 297.
22 I. Neda, H.-J. Plinta, R. Sonnenburg, A. Fischer, P. G. Jones and
R. Schmutzler, Chem. Ber., 1995, 128, 267.
23 C. Wieser, D. Matt, J. Fischer and A. Harriman, J. Chem. Soc.,
Dalton Trans., 1997, 2391.
24 M. Stolmàr, C. Floriani, A. Chiesi-Villa and C. Rizzoli, Inorg.
Chem., 1997, 36, 1694.
25 I. Bagatin, D. Matt, H. Thönnessen and P. G. Jones, Inorg. Chem.,
1999, 38, 1585.
26 M. Vézina, J. Gagnon, K. Villeneuve, M. Drouin and P. D. Harvey,
Chem. Commun., 2000, 1073.
27 C. Loeber, D. Matt, P. Briard and D. Grandjean, J. Chem. Soc.,
Dalton Trans., 1996, 513.
28 C. Wieser, D. Matt, L. Toupet, H. Bourgeois and J.-P. Kintzinger,
J. Chem. Soc., Dalton Trans., 1996, 4041.
29 C. Wieser and D. Matt, Platinum Met. Rev., 1998, 42, 2.
30 C. Wieser-Jeunesse, D. Matt and A. De Cian, Angew. Chem., Int.
Ed., 1998, 37, 2861.
Crystal data. C44H56AgBF4O11P2, M = 1017.55, ortho-
rhombic, space group Pccn, colourless crystals, a = 11.9325(2),
b = 17.6619(2), c = 21.2455(3) Å, U = 21.2455(3) Å3, Z = 4,
µ = 0.588 mmϪ1. Data were collected on a Nonius KappaCCD
diffractometer (graphite-monochromated Mo-Kα radiation,
0.71073 Å) at Ϫ100 ЊC. 39738 Reflections collected, 4299 with
I > 3σ(I). The structure was solved by direct methods and
refined anisotropically on F2 using the OpenMoleN pack-
age.51 Hydrogen atoms were included using a riding model or
rigid methyl groups. Final results: R(F ) = 0.049, wR(F ) = 0.062,
312 parameters.
CCDC reference number 151653.
See http://www.rsc.org/suppdata/dt/b0/b009005k/ for crystal-
lographic data in CIF or other electronic format.
31 B. R. Cameron, F. C. J. M. van Veggel and D. N. Reinhoudt, J. Org.
Chem., 1995, 60, 2802.
32 C. Jaime, J. de Mendoza, P. Prados, P. M. Nieto and C. Sánchez,
J. Org. Chem., 1991, 56, 3372.
33 C. B. Dieleman, C. Marsol, D. Matt, N. Kyritsakas, A. Harriman
and J.-P. Kintzinger, J. Chem. Soc., Dalton Trans., 1999, 4139.
34 C. Loeber, C. Wieser, D. Matt, A. De Cian, J. Fischer and L. Toupet,
Bull. Soc. Chim. Fr., 1995, 132, 166.
35 F. Agbossou, J.-F. Carpentier and A. Mortreux, Chem. Rev., 1995,
95, 2485.
36 A. Bader and E. Lindner, Coord. Chem. Rev., 1991, 108, 27.
37 E. Lindner and H. Norz, Chem. Ber., 1990, 123, 459.
38 R. W. Wegman, A. G. Abatjoglou and A. M. Harrison, J. Chem.
Soc., Chem. Commun., 1987, 1891.
39 V. V. Grushin, J. Am. Chem. Soc., 1999, 121, 5831.
40 M. Sawamura and Y. Ito, Chem. Rev., 1992, 92, 857.
41 C. Dieleman, S. Steyer, C. Jeunesse, D. Matt and A. De Cian,
unpublished results.
42 B. Demerseman, R. Le Lagadec, B. Guilbert, C. Renouard, P.
Crochet and P. H. Dixneuf, Organometallics, 1994, 13, 2269.
43 M. Camalli, F. Caruso, S. Chaloupka, P. N. Kapoor, P. S. Pregosin
and L. M. Venanzi, Helv. Chim. Acta, 1984, 67, 1603.
44 F. J. Parlevliet, M. A. Zuideveld, C. Kiener, H. Kooijman, A. L.
Spek, P. C. J. Kamer and P. W. N. M. van Leeuwen, Organometallics,
1999, 18, 3394.
Acknowledgements
We are grateful to Johnson Mathey for a generous loan of
precious metals.
References
1 V. Böhmer, Angew. Chem., Int. Ed. Engl., 1995, 34, 713.
2 C. D. Gutsche, Calixarenes Revisited, Monographs in Supra-
molecular Chemistry, ed. J. F. Stoddart, The Royal Society of
Chemistry, Cambridge, 1998.
3 A. Arduini, A. Pochini, S. Reverberi, R. Ungaro, G. D. Andreetti
and F. Ugozzoli, Tetrahedron, 1986, 42, 2089.
4 D. M. Roundhill, Prog. Inorg. Chem., 1995, 43, 533.
5 J. M. Harrowfield, M. Mocerino, B. J. Peachey, B. W. Skelton and
A. H. White, J. Chem. Soc., Dalton Trans., 1996, 1687.
6 P. D. Beer, M. G. B. Drew, D. Hesek and K. C. Nam, Chem.
Commun., 1997, 107.
7 M. R. Yaftian, M. Burgard, C. Wieser, C. B. Dieleman and D. Matt,
Solvent Extr. Ion Exch., 1998, 1131.
8 M. J. Marsella, R. J. Newland, P. J. Carroll and T. M. Swager, J. Am.
Chem. Soc., 1995, 117, 9842.
9 P. D. Beer, Chem. Commun., 1996, 689.
10 M. Kawaguchi, A. Ikeda and S. Shinkai, J. Chem. Soc., Perkin
Trans. 1, 1998, 179.
11 G. Arena, A. Casnati, A. Contino, G. G. Lombardo, D. Sciotto and
R. Ungaro, Chem. Eur. J., 1999, 5, 738.
12 P. D. Beer, P. A. Gale and G. Z. Chen, J. Chem. Soc., Dalton Trans.,
1999, 1897.
13 C. Wieser, C. B. Dieleman and D. Matt, Coord. Chem. Rev., 1997,
165, 93.
45 C. D. Gutsche and M. Iqbal, Org. Synth., 1989, 68, 234.
46 A. Casnati, A. Pochini, R. Ungaro, C. Bocchi, F. Ugozzoli, R. J. M.
Egberink, H. Strijk, R. Lugtenberg, F. de Jong and D. N.
Reinhoudt, Chem. Eur. J., 1996, 2, 436.
47 W. Z. Wegener, Z. Chem., 1971, 11, 262.
48 E. W. Abel, M. A. Bennett and G. Wilkinson, J. Chem. Soc., 1959,
3178.
49 J. Powell and B. L. Shaw, J. Chem. Soc. A, 1967, 1839.
50 M. A. Bennett, T.-N. Huang, T. W. Matheson and A. K. Smith,
Inorg. Synth., 1982, 21, 75.
14 O. V. Ozerov, N. P. Rath and F. T. Ladipo, J. Organomet. Chem.,
1999, 586, 223.
15 P. Molenveld, J. F. J. Engbersen and D. N. Reinhoudt, Eur. J. Org.
Chem., 1999, 3269.
51 OpenMoleN, Interactive Structure Solution, Nonius B.V., Delft,
1997.
892
J. Chem. Soc., Dalton Trans., 2001, 881–892