Long tailed cage amines: Synthesis, metal complexation, and structure

Article abstract of DOI:10.1039/b921930g

The generation of amphiphiles derived from macrobicyclic hexamines of the "sarcophagine" class can be prepared through efficient and selective reactions involving the reductive alkylation, using long-chain aldehydes, of amino-functionalised sarcophagines when bound to Cu(ii) or Mg(ii). The Mg(ii) pathway is particularly convenient for the ultimate isolation of the free ligands, which can then be used to form metalloamphiphiles with a variety of metal ions. Structural studies have been made of one of the free (protonated) ligands and some of their complexes.

Full text of DOI:10.1039/b921930g

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Long tailed cage amines: Synthesis, metal complexation, and structure†
a
b
a
a
a
Birger Dittrich,‡ Jack M. Harrowfield, George A. Koutsantonis,* Gareth L. Nealon and Brian W. Skelton
Received 20th October 2009, Accepted 22nd January 2010
First published as an Advance Article on the web 22nd February 2010
DOI: 10.1039/b921930g
The generation of amphiphiles derived from macrobicyclic hexamines of the “sarcophagine” class can
be prepared through efficient and selective reactions involving the reductive alkylation, using
long-chain aldehydes, of amino-functionalised sarcophagines when bound to Cu(II) or Mg(II). The
Mg(II) pathway is particularly convenient for the ultimate isolation of the free ligands, which can then
be used to form metalloamphiphiles with a variety of metal ions. Structural studies have been made of
one of the free (protonated) ligands and some of their complexes.
Introduction
highly lipophilic groups, although this property is also strongly
16
dependent on the counteranion. It was for this reason that
we chose to explore further the synthesis of free cages with
long alkyl-group substituents, ultimately with an emphasis on
Amphiphiles incorporating a complexed metal ion centre, metal-
losurfactants, are expected to find various specific applications,
known examples including those as components of luminescent
and magnetic materials, as catalysts and as MRI agents. In
1
2
chains of length C or greater, since the amphiphilicity of such
7
3
4
5
species (especially in their complexes) was expected to be most
pronounced. Three methods that have proven successful for
the synthesis of some such ligands in their complexed form
the particular instance of the macrobicyclic hexamines termed
6
“
sarcophagines” (Fig. 1) as the metal binding unit, relatively
simple functionalisation has been shown to lead to amphiphiles
7,8
7,8,17,18
are diazotization and reductive alkylation (amination)
of
7
-9
with properties as diverse as those as vermicides, as chiral anion
amino-substituted cage complexes, and variations on the original
10
11
sensors and as photo- and electro-catalysts. Such amphiphiles
may also have the advantage of control of the form of their
8,9
template synthesis. These have employed very largely Co(III)
reactants, advantageously because of the protection of the six N-
donors within the macrobicycle but disadvantageously in many
instances because of the reduction of the nucleophilicity of
pendent groups involved in the substituent introduction and the
consequent need for the use of alkylating agents in large excess.
Another major drawback to functionalising Co(III) cages is the
difficulty in removing the metal ion from the complex after
12,13
association through changes in overall charge.
is known that a wide range of metal ions can be used to form
kinetically inert sarcophagine complexes and that these complexes
Given that it
1
4
are, for example, redox active over a total potential range of >2 V,
it remains an intriguing prospect to incorporate this wider range
of metal ions into sarcophagine surfactants which have been, up
to now, predominantly Co(III) derivatives. This implies the need
for synthesis of the free ligands and the objective of the present
work was thus to optimise, on the basis of varied preliminary
observations, techniques for the preparation and isolation of alkyl-
functionalised metal-free sarcophagines (Fig. 1) as one pathway
to a new group of metallosurfactants.
modification, this requiring rather stringent conditions in general
19,20
and sometimes proving to be impossible.
In the face of such
problems, it has been found that M(II) complexes of amino-
functionalised cages are considerably stronger nucleophiles than
their Co(III) analogues and that the use of Mg(II) in particular
allows very ready isolation of the ligands from the product
A variety of methods are known for introduction of lipophilic
substituents onto a sarcophagine unit but many of these involve
aromatic entities which generally prove to reduce the solubility
of the complexes in all solvents. With long alkyl chains, the
solubility in water is diminished (often dramatically) and solubility
in apolar solvents can be achieved through the introduction of
complexes, a procedure already developed for the synthesis of
17
free cage ligands with C13
H
27 substituents. The present work is
a systematic exploitation of these developments for the synthesis
of new amphiphilic cages using reductive alkylation of aminocage
reactants (Fig. 1). The choice of different reactant species has
enabled efficient and selective syntheses of mono- and di-alkylated
cages to be developed.
15
a
Chemistry, M313, School of Biomedical, Biomolecular and Chemical
Sciences, The University of Western Australia, Crawley, 6009, Australia.
E-mail: george.koutsantonis@uwa.edu.au
Institut de Science et d’Ing e´ nierie Supramol e´ culaires, Universit e´ de Stras-
bourg, 8, all e´ e Gaspard Monge, 67083, Strasbourg, France
Results and discussion
b
It is known that the free diaminosarcophagine ligand, (NH
2
2
) sar
†
Electronic supplementary information (ESI) available: Details of the
(
L2), reacts with alkylating agents, including aldehydes used in
2+
2+
synthesis of [Cu(C
and reductive demetallation of [Cu(C
8
H
17NH)
2
sar] and [Cu{(C
7
H
15
)
2
2
N}(C
7
H
15NH)sar]
and
+
reductive alkylation procedures as presently employed, to give
mixtures of species alkylated at both the primary and secondary
N-centres, though with the latter predominating. It was hoped
initially that both this lack of selectivity and the preference for
secondary-N alkylation might be overcome by the use of the
partly protonated ligand (assuming preferential protonation of
7
H
15NH)
2
sar] with NaBH
4
Pd/C are reported. CCDC reference numbers 688325 [L1], 738804
L7], 738801 [CuL4], 738802 [Cu(HL4)], and 738803 [ZnL5]. For ESI
and crystallographic data in CIF or other electronic format see DOI:
[
17
1
0.1039/b921930g
‡
Current address: Georg-August-Universit a¨ t, Institut f u¨ r Anorganische
Chemie, Tammannstr. 4, D-37077 G o¨ ttingen, Germany.
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Fig. 1 Structures of the macrobicyclic ligands used and produced in this work.
secondary sites), as has proved successful in the reactions of
always gave mixtures of the two products and some starting
material. While the properties of the Cu(II) complexes of mono-
21
some aminomonomacrocycles, but this was not so. In fact, there
is structural evidence that protonation of the primary sites in
17
and di-tridecylated (NH
2
2
) sar are markedly different, present
22
(
NH
2
)
2
sar occurs early in the sequence of protonation steps and
investigations of the use of chromatography (on silica, alumina or
cation exchange columns) or fractional crystallisation to separate
the product mixtures for this and other chains showed such
methods to be tedious and inefficient. Fortunately, however, it was
found possible to adapt the reaction conditions so as to obtain the
while this strictly concerns the solid state, it is plausible that in
solution also, protonation of the primary sites would provide the
maximum distance between similarly-charged cationic centres.
(
symmetrically 1,8-) di-alkylated derivatives alone in good yield.
Cu(II) complexes
Thus, for octanal as the aldehyde, for example, use of a 6 : 1 octanal
to cage ratio under refluxing conditions in EtOH allowed the ex-
clusive isolation of [Cu(C
via MS) after 30 min by precipitation from the reaction mixture by
the addition of HClO . Higher alkylation products could also be
Mixtures of alkylation products, though here involving just the ini-
tially primary amino-group sites, were also obtained in preliminary
experiments to conduct reductive alkylation of the Cu(II) complex
8
H
17NH)
2
sar](ClO
4
)
2
·xHClO
4
(identified
2
+
of (NH
2
)
2
sar, [Cu(NH
2
)
2
sar] (CuL2), used as a species where
4
these external amino substituents are known to be moderately
prepared using greater excesses of aldehyde in the reaction mixture
(Scheme 1, also see ESI†).
An obvious solution to the problem of inefficient formation of
monoalkylated cage ligands in competition with higher alkylated
species is to use a reactant cage but with a single alkylation site.
19
nucleophilic. Reactions were performed in EtOH in the presence
of molecular sieves, NaBH CN, and acetic acid, conditions known
3
7,17
to be effective in related syntheses and less harsh than those
seemingly required for complete formation of the intermediate
imines followed by NaBH
to cage ratios of 1 : 1 and 2 : 1 in an attempt to maximise the
yields of mono-alkylated and di-alkylated species, respectively,
4
reduction. Initial work using aldehyde
This is available in the cage ligand (CH
3
)(NH
2
)sar (L1), formed
23
3+ 24
via template synthesis on the complex [Co(sen)] . The synthesis
4
+
of [Co(CH
3
)(NH )sar] is somewhat more laborious than that of
3
Scheme 1 The various products identified (via MS) during reductive alkylation procedures on CuL2 (R = alkyl group).
434 | Dalton Trans., 2010, 39, 3433–3448
3
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2
Scheme 2 Isolation of L1·4HCl·2H O using hot, concentrated HCl under pressure.
5
+
[
3 2
Co(NH )
sar] but the real disadvantage here was that the use of
2
2
25
excess cyanide to isolate L1 gave rather poor yields. It was of
interest, therefore, to investigate another method for obtaining L1
in the hope of increasing the yield of this rather precious starting
material.
Using a procedure analogous to that for the isolation of
2
2
3+
[
(NH
3
)
2
sarH
3
]Cl
5
·4H
2
O, [Co(CH
3
)(NH
2
)sar] was reduced to
2
+
the more labile [Co(CH
3
)(NH
2
)sar] in deoxygenated water using
Zn dust under an inert atmosphere (Scheme 2). After filtration and
removal of the solvent under vacuum, deoxygenated concentrated
HCl was added to the solid, the flask was sealed and the mixture
◦
heated to 140 C for at least 12 h. The progress of the reaction
was readily observed visually, as the dull green colour of the
initially largely insoluble Co(II) cage complex gave place to the
2
-
characteristic deep blue colour of [CoCl
workup using cation exchange chromatography on Dowex, the
protonated ligand [(CH )(NH )sarH ]Cl O)
4
]
in solution. After
Scheme 3 Synthesis of mono-alkylated Cu-cage complexes. (R = C10
21
H ,
13
C H27, C14H29).
3
3
3
4
·2H
2
O (L1·4HCl·2H
2
could be isolated in 60–70% yield. Preparation of the Cu(II)
and Mg(II) complexes of L1 was readily achieved by heating an
aqueous solution of the hydrochloride with a basic metal source
completely removing the metal from the complex (Scheme 5, also
see ESI†).
Thus, selective preparation of mono- and di-alkylated cage
ligands could be achieved using Cu(II) complexes during the
syntheses. Following the progress of the reactions of these param-
agnetic complexes was, however, inconvenient, and a significant
drawback was the difficulty of removing the ligands from the
metal. Ultimately, these observations on the Cu(II) complexes were
exploited in the development of more convenient syntheses of the
free di-alkylated ligands based on the use of Mg(II) complexes.
(
“CuCO
3
” or MgO) followed by precipitation.
Despite the presence of but a single, weakly nucleophilic “exter-
2
+
nal” amino group in the complex [CuL1] , the use of large excesses
of aldehyde and elevated temperatures in an attempt to maximise
the yield of the mono-alkylated product proved ineffective as it led
to di-alkylation and subsequent tedious separations. Fortunately,
under milder conditions such as the use of one to two equivalents
of aldehyde, the mono-alkylated products could be obtained in
6
0–70% yields (Scheme 3).
Since the Cu(II) complexes were extremely resistant to ligand
Mg(II) cages
removal by treatment with acid, they were first subjected to
Success in the selective synthesis of mono- or di-alkylated Cu(II)
cages provided the stimulus to examine the use of a more labile
and diamagnetic metal complex such that the “free” ligands could
be obtained relatively easily. Magnesium(II) cage complexes are
appropriate in this respect, as they allow for the reactions to be
monitored via NMR spectroscopy and are known to dissociate
26
transmetallation with Zn metal. It was anticipated that the
Zn(II) complex could then be demetallated by treating the
27
complex with acid, thus liberating the protonated free ligands.
However, heating solutions of either the mono- or di-alkylated
copper complexes in the presence of Zn metal gave very sluggish
reduction of the Cu(II) complex, as judged from the colour
in solution, and even after extended reaction times a faint
tinge of blue colour was always observed in solution, indicating
incomplete reduction of the Cu(II) complex during the reaction
17
readily in acidic solution thus allowing the alkylated ligands to
be readily demetallated by lowering the pH. However, the lability
of the Mg(II) complexes in acid is a potential drawback when
considering their use in reductive alkylation reactions as these
are typically performed at pH ~ 6–8, in order that rapid and
selective reduction of the C=N double bond of the protonated
(
Scheme 4) or perhaps the presence (unexpected) of a stable Cu(I)
species.
Ultimately, an alternative method using NaBH
28
4
and Pd/C
imine intermediate (rather than the carbonyl group of any free
-
to reduce the Cu(II) species was found to be more effective at
aldehyde) is achieved with [BH
3
CN] , but successful reductive
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Scheme 4 Attempted reduction of Cu(II) complexes with Zn, and subsequent demetallation under acidic conditions. (A = CH
3
or NHR; R = alkyl
group).
in MeOH or MeOH–CHCl (Scheme 7). Removal of magnesium
3
from the alkylated cage was achieved by heating the material in
concentrated HCl/MeOH or HCl/EtOH, and isolation of the
metal free ligands was achieved after chromatography on Dowex
cation exchange resin followed by recrystallisation to give the pure
ligands in ca. 55–65% yields.
The mono-alkylated ligands L3 and L5 exhibit good solubility
in water as their hydrochloride salts, displaying typical surfactant
properties such as their propensity to form stable aqueous foams
when agitated. The ability to form foams is lost upon symmetrical
di-alkylation to give L6, which also coincides with a reduction
in water solubility. The long chained derivative L7 did not display
any significant solubility in water, but showed favourable solubility
in the polar alcoholic solvents MeOH and EtOH. Thus, it appears
that the introduction of significant apolar groups, in this case
the addition of two C14 tails on the ligand, is required to effect
a meaningful change in the aqueous solubility of the free cage.
However, even after dialkylation, the polar charged cage moiety
still exerts a strong influence on the solubility of the ligand,
favouring polar solvents, and it appears that the introduction of
more lipophilic groups is required to achieve solubility in non-
Scheme 5 Reduction of the copper complexes with NaBH
give the free ligands. (A = CH or NHR; R = alkyl group).
4
and Pd/C to
3
alkylation has been achieved under more basic conditions in
29
other systems. There is, of course, a compensating factor that
attack of a hydridic nucleophile on a pendent imine should be
facilitated by the cationic charge. Thus, the reductive alkylation of
MgL2·(OAc)
basic conditions. NMR spectroscopic experiments indicated that
to give the desired mono-alkylated
2
and MgL1·(OAc)
2
was investigated under weakly
16
polar solvents.
alkylation of MgL1·(OAc)
2
With these solubility properties in mind, synthesis of metal
complexes from the free ligands is a relatively straightforward
process, owing to the rapid complexation kinetics and stability of
species was readily achieved using 4–5 molar equivalents of the
-
aldehyde in the presence of an excess of [BH
3
CN] at room
22
temperature (Scheme 6). The synthesis of the symmetrically di-
alkylated complexes was performed in an analogous manner, via
reductive alkylation of MgL2 with 8 molar equivalents of aldehyde
complexes of the cage amines. Since the ligands were isolated
in their protonated forms (L3·5HCl, L5·7HCl, L6·4HNO
L7·4HCl·2H O), it was convenient to simply heat the ligand with a
3
,
2
Scheme 6 Synthesis of the mono-alkylated ligands using 4–5 : 1 aldehyde to cage ratios. (R = C10
H21, C14H29).
3
436 | Dalton Trans., 2010, 39, 3433–3448
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Scheme 7 Synthesis of the dialkylated ligands using 8 : 1 aldehyde to cage ratios. (R = C
7
H15, C14H29).
basic metal source such as a metal carbonate or acetate in
a suitable solvent (water or MeOH), with oxygenation of the
solutions required for the reactions with cobalt in order to oxidise
the Co(II) to Co(III). This procedure is suitable for the metal
complexes targeted (Cu, Ni, Zn and Co) but not general for
30
all possible metal complexes of the ligand. After filtration of
any undissolved carbonate, the compounds were converted to
their acetate salts (in order to avoid the potential complication
of precipitating the complexes as mixed salts (i.e. mixture of
-
-
15,19
Cl /ClO
4
anions) ) by ion exchange on Dowex 1 ¥ 8 anion
exchange resin before being precipitated by the addition of
perchloric acid. The only exception to this procedure was in the
case of CoL7, where the product readily precipitated from the
reaction mixture as the tri-chloride, allowing straightforward
recovery of the complex.
The complexes displayed similar solubility characteristics to
their ligand precursors. The mono-alkylated species exhibit good
solubility in water as their acetate salts, and produced stable foams
when agitated, but the addition of chloride, perchlorate or nitrate
anions decreased their solubility in polar solvents significantly.
The di-alkylated complexes derived from L6 also exhibited good
solubility in water as their acetates, but did not foam when
agitated, as was observed for the ligand precursor. Unsurprisingly,
complexes of the longer chain di-alkylated ligand L7 proved to be
completely insoluble in water, regardless of the anion present, and
were most readily dissolved in MeCN. As part of our continuing
16
efforts to prepare metallomesogens, the thermotropic properties
of these complexes were examined with a polarising optical
microscope fitted with a hot stage, but unfortunately none of the
complexes displayed any mesophases prior to decomposition. The
surfactant properties of these complexes, including any lyotropic
liquid crystalline behaviour are currently under investigation.
Single crystal X-ray structure determinations of L1, L7, CuL4,
Cu(HL4) and ZnL5
The lattice of the crystalline ligand hydrochloride
7
L1·4HCl· /
3
H O, while complicated to describe in detail, shows
2
that the tetra-protonated ligand is like analogous derivatives of
Fig.
L1·4HCl· /
2
(a) Molecular projection of one ligand molecule of
2
2
(
NH
2
)
2
sar in adopting a form poised for reception of a metal
7
7
3
H
2
3 2
O. Unit Cell of L1·4HCl· / H O. (b) Layers in the ac plane
ion by binding to the six secondary-N centres (Fig. 2(a)). In
detail, the structure is remarkable for the fact that there are 24
molecules within the unit cell, the subtle differences between
with pairs of different molecules (1,2 and 3,4, and 5,6) aligned parallel to
the a axis. H-atoms omitted for clarity. (c) One of the layers from the ac
plane. H-atoms omitted for clarity.
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Fig. 3 (a) Projection of the cation of L7·4HCl·2H
2
O·2CH
3
OH. (b) Unit cell diagram for L7·4HCl·2H
2
O·2CH
3
OH projected down the a axis.
them being associated with conformational changes presumably
consequential upon differences in H-bonding interactions. The
differences are not due to inversion of configuration at any of
the three (unprotonated) chiral N centres. The molecules are
packed in the unit cell in layers in the ac plane with pairs of
different molecules (1,2 and 3,4, and 5,6) aligned parallel to the
a axis (see Fig. 2(b) with one layer shown in Fig. 2(c)). All of
the molecules in the same layer are aligned with respect to the
apical substituents. As could be expected there is present an
extensive three dimensional hydrogen bonding array, involving
most of the available hydrogen atoms, and is best visualized
in silico.
the NH groups of the cage itself are involved in close contact
˚
with chloride anions (HN ◊ ◊ ◊ Cl 3.31–3.47 A), the other two in
˚
close contact with water molecules (HN ◊ ◊ ◊ O 2.73–2.80 A), with
the nitrogens of both apical substituents interacting with two
˚
chloride anions each (HN ◊ ◊ ◊ Cl 3.08–3.17 A). This shows that
the anions are acting to link the cages together in an intricate
H-bonding network between the chlorides and solvent molecules.
The packing of the ligand within the solid can be described as
homochiral sheets of protonated cages, anions and solvent, with
adjacent sheets alternating in chirality of the cage in a DKDK
manner, separated by sheets of aliphatic tail groups, forming a
herringbone type arrangement when viewed down a (Fig. 3(b)).
The tails exist in a fully trans-extended arrangement, except for
a gauche conformation for the first two carbons of the chain
immediately attached to the apical nitrogen of the cage caps. The
angle between the two apical chains as defined by the C(12)–C(113)
The structure of the cation present in L7·4HCl·2H
2
O·2CH
3
OH
is shown in Fig. 3(a) and is one of the few structures obtained
2
2,27
on substituted, metal-free sarcophagines.
As observed in the
6
solid state structures of some M(II) complexes of (NH
2
) sar, as
2
22
◦
well as the free ligand and its various protonated forms, the cage
core of the ligand adopts a conformation intermediate between
octahedral and trigonal prismatic, with an average twist angle
and C(11¢)–C(1C¢) vectors is 26.8 . The angles between these and
the axis of the cage, as defined by the N(0)–N(1¢) vector, are 20.0
◦
and 31.6 .
◦
of 27 . Two protons are encapsulated by the cage, whereby a
The packing of the tails within the lattice is a mixture of two
modes, one in which two alkyl groups from adjacent sheets meet
in an end-on manner, and the other in which the tails of adjacent
sheets lie in a roughly parallel sheet-like arrangement. Dispersion
interactions play a role in the packing of the lattice, with the alkyl
hydrogen on the protonated nitrogen of a given cap is involved in
a bifurcated H-bonding arrangement with the other two nitrogens
◦
˚
of the cap (H ◊ ◊ ◊ NH 2.20–2.45 A). The twist angle of 27 places the
NH units of the cage itself too far apart to coordinate an anion
31
˚
(
as is commonly observed in Co(III) complexes of the ligand),
chains displaying closest contacts (C ◊ ◊ ◊ C 3.8–3.9 A) for parallel
˚
and thus the “external” NH groups, including those of the cap
substituents, act as donors to separate acceptors. Thus, four of
tails of adjacent cation sheets, and (C ◊ ◊ ◊ C 4.0–4.1 A) within any
given sheet.
3
438 | Dalton Trans., 2010, 39, 3433–3448
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Fig. 4 (a) Projection of the cation of CuL4. Only one component of the disordered atoms is shown in this figure and in Fig. 4(b). (b) Unit cell of CuL4
projected down the a axis. H-atoms omitted for clarity.
Compound CuL4 crystallised from a dilute solution in water as
the di-perchlorate and the coordination geometry about the Cu(II)
ion is irregular and distorted, reflecting Jahn–Teller distortion
enantiomers throughout the sheets. The packing of the molecules
is (head–head–tail–tail),
in the crystal lattice of CuL4·(ClO
4 2
)
with the tails adopting an essentially transoid arrangement, and
serve to link adjacent polar sheets via interdigitation with their
associated tails, which display some close contacts of (C ◊ ◊ ◊ C ca.
32
consistent with other known Cu(II) cage complexes (Fig. 4a). It
should be noted that the model for this structural determination
can be considered poor, as a result of twinning, and conclusions
reached should be considered tenuous. An emerging theme for
˚
3.9–4.0 A) indicative of relatively weak dispersion interactions.
The perchlorate anions are located in sheets above and below
the planes defined by the copper atoms within any given sheet.
Perchlorates located nearest the methyl capped end of the cage
serve to link three nearest neighbour cages together via hydrogen
17,18
alkylated cage species
is found by considering the structure
as sheets of cations and anions separated by sheets of aliphatic
tails when viewed down a (Fig. 4b), with an equal distribution of
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Fig. 5 (a) Projection of the cation of Cu(HL4)·(ClO
4
)
3
·2H
2
O showing one component of the disordered atoms only. (b) Unit cell contents of
Cu(HL4)·(ClO ·2H
4
)
3
2
O projected down the a axis showing all disordered atoms. H-atoms omitted for clarity.
1
8
˚
in the lattice for the shorter chain complex ZnL3 by producing
a polar crystal, and thus it was of interest to determine what
effect it would have here. In the case of CuL4, protonation to
bonding with coordinated –NH-groups (O ◊ ◊ ◊ NH ca. 3.0–3.4 A).
The other sheet of perchlorates links three nearest neighbour cages
via close contacts with two coordinated –NH-groups (O ◊ ◊ ◊ NH
˚
give Cu(HL4)·(ClO
4
)
3
·2H
2
O (see Fig. 5) has a more subtle effect
ca. 3.2–3.5 A) and a relatively remote contact to the unprotonated
apical –NH-group (O ◊ ◊ ◊ NH ca. 3.6–3.9 A). There are few close
contacts between individual sheets of antiparallel cages, except
for some relatively remote carbon–carbon contacts between the
˚
on the overall lattice, as the (head–head–tail–tail) arrangement
of the cations is still present, but there is a significant bend of
the tail away from the plane defined by the headgroup slabs, as
seen for ZnL3. The tails do not appear to be involved in any
significant interactions with one another, and thus the bend in the
chain between C2 and C3 is again most probably a consequence
cage methyl group of one sheet and the cap methylenes of another
˚
(
C ◊ ◊ ◊ C ca. 3.9–4.0 A). Protonation of the uncoordinated nitrogen
is known to have a dramatic effect on the packing of the molecules
3
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Fig. 6 (a) Projection of the cation of ZnL5 showing both components of the disordered atoms. (b) Unit cell contents of ZnL5 projected down the a axis.
H-atoms omitted for clarity.
of the need to accommodate the extra anion within the headgroup
region of the lattice, causing the cages to adopt a more nearly
parallel arrangement.
and difficult separations. The preparation of mono-alkylated
species is facilitated by the development of a high yielding synthesis
of the free ligand L1, which will enable further exploitation of this
useful ligand in future. Successful protection of the secondary
amine centres has been achieved through coordination to a metal
centre, with Mg(II) being preferred to Cu(II) due to the relative ease
of monitoring the reaction progress and subsequent removal of the
metal ion to give the desired free ligands. This method should
be of tremendous utility in the preparation of functionalised
free cage ligands, allowing for the facile exploitation of the
numerous possible transition metal-sarcophagine complexes. This
was demonstrated in the present case by the preparation of
metal complexes (i.e. Co(III), Zn(II), Cu(II) and Ni(II)) of the new
alkylated ligands in a simple and efficient manner.
The complex ZnL5 (see Fig. 6) crystallised from water as the
di-perchlorate and the coordination geometry about the Zn(II) ion
is intermediate between octahedral and trigonal prismatic, with an
◦
average twist angle of 32 . The arrangement of the molecules in
the lattice is similar to that observed in the case of CuL4, with the
now familiar (head–head–tail–tail) arrangement of the cations to
form polar sheets separated by apolar tails. The tails are almost
fully trans extended, displaying very little close contact with other
apolar units, except for a remote contact with cage methylene
˚
groups (C ◊ ◊ ◊ C 4.0 A), and the perchlorate anions serve to link
the cage headgroups in a similar manner to that observed in the
˚
structure of CuL4, displaying close contacts (HN ◊ ◊ ◊ O 3.2–3.5 A).
The introduction of alkyl groups to the sarcophagines reduces
the aqueous solubility of their complexes relative to their simple
cage precursors, but only in the case of the complexes of the di-
alkylated C14 ligand L7 was solubility in water drastically reduced.
The mono-alkylated species display typical surfactant behaviour
(by forming stable aqueous foams), which is lost upon symmetrical
1,8-di-alkylation. Examination of the structures of the compounds
Conclusions
Efficient methods have been developed that allow for the selective
preparation of mono- and di-alkylated cage complexes by careful
control over the reaction conditions, obviating the need for tedious
This journal is © The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 3433–3448 | 3441

View Article Online
◦
in the solid state indicate that both of the free ligands L1 and L7
display cage moieties poised for reception of a metal ion, and the
packing of the cations in L7, CuL4, CuHL4 and ZnL5 exhibit
a common theme whereby the polar and apolar moieties form
alternating layers, reminiscent of a bilayer arrangement.
and the stirred mixture heated to 140 C using a heater stirrer
and an oil bath (CAUTION: This reaction must be conducted
behind a suitable blast shield). The solution colour became deep
blue within 1 h but heating was continued for 18 h to ensure
equilibration. On cooling, the solution was exposed to the normal
atmosphere, diluted to 1 L with water and passed through a
column of Dowex 50W¥2 cation exchange resin, this procedure
allowing retention of the protonated ligand and a small amount
of unreacted complex (now in its Co(III) form), with much of
Experimental
Safety note
-
1
the released Co(II) passing through. Elution with 1 mol L HCl
500 mL) removed any residual Co(II) and the column was then
washed with water (500 mL) before the ligand was removed by
elution with 0.2 mol L NaOH (1 L). The ligand eluate was
acidified with glacial acetic acid and reapplied to a column of
Perchlorate salts are potentially explosive. Although no problems
were experienced with the compounds synthesised in this work,
they should never be handled in large quantities, heated in the
solid state, nor scraped from sintered glass frits.
(
-1
+
H form Dowex 50W¥2 cation exchange resin, which was washed
General
-1
with water (500 mL) and then 1 mol L HCl (500 mL) to
+
-1
remove Na , and finally with 5 mol L HCl (1 L) to remove
the ligand hydrochloride. This final eluate was taken to near-
dryness under vacuum before ethanol was added to precipitate the
Nuclear magnetic resonance (NMR) spectra were acquired using
1
13
Bruker ARX 300 ( H at 300 MHz and C at 75.5 MHz), Bruker
1
13
AV 500 ( H at 500.13 MHz and C at 125.8 MHz), or Bruker
AV 600 ( H at 600.13 MHz and C at 150.9 MHz) instruments.
All carbon spectra were proton decoupled. Chemical shifts for
-
1
1
13
crude product. Recrystallisation from hot 3 mol L HCl by the
addition of ethanol gave colourless, weakly hygroscopic crystals of
[(CH
3
)(NH
3
)sarH
71%). H NMR (D
(m, 24H, cage–CH -). C NMR (D
7.14 (C of methyl cage cap), 46.42, 48.32, 50.63, 54.12 (cage–CH -
3
]Cl
4
·2H
2
O (L1·4HCl·2H
2
O) (5.80 g, 12 mmol,
), 3.1–3.5
O, 75 MHz): d 19.41 (-CH ),
samples measured in D
internal standard of acetone which was taken as being 2.22 for H
NMR spectra and 30.89 for C NMR spectra relative to TMS.
Chemical shifts for samples measured in d -DMSO, CDCl and d -
2
O are expressed in ppm relative to an
1
1
2
O, 300 MHz): d 1.0 (s, 3H, -CH
3
1
3
1
3
2
2
3
3
2
6
3
3
)
, 56.62 (C of amine cage cap). MS(ES) (m/z): 314.3 [C15
H
35
N +
7
MeCN were referenced to the residual solvent peak. Assignments
were made with the aid of either the DEPT or HSQC techniques.
Mass spectra were recorded using the electrospray (positive ion
trap) or fast-atom bombardment technique on a VG Autospec
instrument or QSTAR XL-MS/MS.
+
2+
H] ; 157.5 [C15
H
35
N
7
+ 2H] . Anal. Calcd for C15
H
43
N
7
Cl
4
2
O :
C, 36.37; H, 8.75; N, 19.79. Found C, 36.67; H, 8.53; N, 19.70.
Crystals suitable for an X-ray structure determination were grown
by addition of EtOH to a hot 3 M HCl solution of the ligand
followed by slow cooling. The structure solution was modelled as
Microanalyses for C, N, and H were carried out by The Aus-
tralian National University Microanalytical Service. All samples
L1·4HCl·7/3H
Mg(CH )(NH
MgO (0.08 g, 2.0 mmol) was added to
CH )(NH O (0.50 g, 1.0 mmol) in water (ca.
)sar·4HCl·2H
0 mL) and the mixture heated on a steam bath for 8 h, with
2
O.
◦
were thoroughly dried under vacuum at 50 C for at least 4 h prior
[
3
3
)sar]Cl
3
·2.5H
2
O
(MgL1·Cl
2
·HCl·2.5H
2
O).
solution of
to their analysis.
a
2
3
[
Co(CH
NH
sar·2H
ature methods. Heptanal, octanal, decanal, tridecanal, NaBH
CN, NaBH (Aldrich), 10% Pd/C (Fluka), Co(CH CO O,
·4H
Cu(CH CO O, CuCO .Cu(OH) , NiCO ·2Ni(OH) ·4H
·H
Ajax), CoCO O, ZnO, MgO (BDH) were all used as
·xH
received. Tetradecanal was synthesised from tetradecanol via
3
)(NH
3
)sar]Cl
4
·0.5H
2
O
(CoL1·Cl
4
·0.5H
2
O)
and
(
3
2
2
22
(
2
)
2
2
O
(L2·2H O) were synthesised according to liter-
2
2
3
-
periodic addition of water to maintain the volume of the solution.
The mixture was then filtered, concentrated to a volume of
ca. 5 mL on the rotary evaporator and cooled on ice as a
few drops of 5 M HCl were added to the solution, followed
quickly by the addition of EtOH to precipitate a white powder
4
3
2
)
2
2
3
2
)
2
2
3
2
3
2
2
O
(
3
2
33
pyridinium chlorochromate (PCC) oxidation. “Absolute” EtOH
which was collected and washed with EtOH then Et
Mg(CH )(NH
.78 mmol, 78%). MS(FAB) (m/z): 372.0 [MgC15
2
O to give
O) (0.38 g,
˚
and MeOH were stored over 3 A molecular sieves prior to use in
[
3
3
)sar]·Cl
3
·2.5H
2
O (MgL1·Cl
2
·HCl·2.5H
2
the following syntheses.
+
0
3
3
H
35
N
7
+ Cl] ;
The synthesis and discussion of the complex ZnL3 are given
+
36.0 [MgC15
H
35
N
7
- H] . Anal. Calcd for MgC15
6.75; H, 8.43; N, 20.00. Found C, 37.05; H, 8.96; N, 19.93. NMR
H
41
N
7
Cl
3
O2.5: C,
18
elsewhere.
spectra of the complex in D
2
O indicated a gradual demetallation
Synthesis
of the ligand, thus a convenient method for obtaining NMR
spectra was to convert the complex to its acetate salt by passing
through a column of Dowex 1 ¥ 8 anion exchange resin (acetate
form) and evaporating to dryness. This material was also more
useful for the subsequent reductive alkylation reactions in alcohol
solvents.
[(CH
3
)(NH
3
)sarH
)(NH
3
]Cl
)sar]Cl
4
·2H
2
O
·0.5H
(L1·4HCl·2H
2
O). Under ar-
O (8.77 g, 17 mmol) was dis-
gon, [Co(CH
3
3
4
2
solved in deoxygenated water (ca. 75 mL) and an excess of Zn
powder (5 g) was added to the orange solution. The solution
colour rapidly changed to a dull green and the mixture was stirred
for 2 h to complete reduction before being filtered via a cannula
1
[Mg(CH
NMR (D
6H, 2(CH
cage–NH-), 3.60 (m, 3H, cage–NH-). C NMR (D
d 23.95 (CH CO ), 23.96 (cage–CH ), 35.71 (C of methyl cage
3
)(NH
O, 600 MHz): d 0.67 (s, 3H, cage–CH
CO )), 2.30–3.20 (m, 24H, cage–CH -), 3.41 (m, 3H,
O, 150 MHz):
2
)sar](CH
3
CO
2
)
2
(MgL1·(CH
3
CO
2
)
2
).
H
ꢀ
R
into a thick-walled 150 mL Schlenk flask fitted with a RotaFlo
2
3
), 1.90 (s,
tap. The solvent was removed under vacuum and replaced with
deoxygenated, conc. HCl (ca. 75 mL), most of the dull green
solid initially remaining insoluble. The tap to the flask was closed
3
2
2
1
3
2
3
2
3
3
442 | Dalton Trans., 2010, 39, 3433–3448
This journal is © The Royal Society of Chemistry 2010

View Article Online
cap), 49.87, 50.09 (cage–CH
2
-), 50.73 (C of amine cage cap),
CO ).
of MeOH/conc. HCl (50 : 50 v:v) and heated at reflux for 5 h. The
solvent was then removed on a rotary evaporator and the solid
residue dissolved in MeOH and applied to a column of H Dowex
5
8.44, 59.09 (cage–CH -), 182.07 (CH
2
3
2
+
[
Cu(CH
HClO ). CuCO
solution of (CH
O (ca. 10 mL), causing immediate effervescence and a deep
3
)(NH
2
)sar](ClO
·Cu(OH)
)(NH
)sar·4HCl·2H
4
)
2
·0.5HClO
(0.60 g, 2.7 mmol) was added to a
O (1.20 g, 2.28 mmol) in
4
(CuL1·(ClO ·0.5-
4
)
2
5
0W¥2 cation exchange resin which was washed successively with
MeOH, H O, 1M HCl, H O, MeOH (500 mL each) and the
ligand was eluted with a mixture of conc. HCl/MeOH (50 : 50 v/v,
00 mL). The solvent was removed on a rotary evaporator giving
4
3
2
2
2
3
2
2
H
2
5
blue colour to appear in the solution. The mixture was heated on a
steam bath for 4 h, filtered and the solution was diluted to 500 mL
with water and applied to a column of H Dowex 50W¥2 cation
an off-white tacky film. Crystallisation of the product was found
to be hampered by the presence of water, so the product was
repeatedly dissolved in MeOH and evaporated to dryness (5
times) and finally the product was crystallised by dissolving in
+
exchange resin. The column was washed with water (500 mL), 1 M
HCl (500 mL) and the complex, now violet in colour, was eluted
from the column with 3 M HCl. The solvent was removed from the
rotary evaporator, leaving a green-brown solid, which persisted
even after repeated evaporation of water. The green-brown solid
was dissolved in water to give a light blue solution, which was
slurried with ca. 5 g of Dowex 1¥8 anion exchange resin (acetate
form) for 15 min before being loaded onto a column of the same
resin. Elution with water removed a deep blue solution, which
was brought to dryness on the rotary evaporator. The blue solid
was dissolved in EtOH (ca. 10 mL), filtered and cooled on ice
hot MeOH, filtering and then allowing to cool to RT before
◦
being stored at -20 C. The solid was collected under N
2
to give
(L3·5HCl) (0.84 g, 1.3 mmol, 59%)
as a semicrystalline white powder. H NMR (D O, 600 MHz): d
), 1.20–1.35 (m, 12H,
-), 1.69 (apparent p, 2H, -
[
(C10
H
21NH
2
)(CH
3
)sarH
4
]Cl
5
1
2
0
.85 (t, 3H, -CH
(-CH -), 1.38 (apparent p, 2H, -CH
-), 3.05–3.45 (m, 26H, (-CH –N + cage–CH
O, 150 MHz): d 14.04 (-CH ), 19.36 (cage–CH
6.69, 28.74, 29.03, 29.05, 29.20, 31.78 (-CH -), 37.00 (C of methyl
cage cap), 43.20 (-CH –N), 46.66, 48.31, 49.35, 54.18 (cage -CH
0.98 (C of amino cage cap). MS(ES) (m/z) 454.29 [C25
3
), 1.00 (s, 3H, cage–CH
3
6
CH
2
2
13
2
2
2
-)). C NMR
), 22.66, 26.23,
(
D
2
3
3
2
2
2
2
-),
+
before conc. HClO
further deposition of a blue solid was observed. The blue solid
was collected, washed with cold EtOH and finally Et O to give
Cu(CH )(NH )sar](ClO
·0.5HClO
0.63 g, 1.0 mmol, 44%). MS(ES) (m/z): 475.17 [CuC15
4
(ca. 4 mL) was added dropwise until no
6
H
N
55
N
7
+
2+
H] ; 227.59 [C25
H
55
N
7
+ 2H] . Anal. Calcd for C25
H
60
7
5
Cl : C,
2
4
7.21; H, 9.51; N, 15.41. Found C, 46.64; H, 8.83; N, 15.41.
[
(
3
2
4
)
2
·0.5HClO
4
(CuL1·(ClO
4
)
2
4
)
[
Co(C10
H
21NH
2
)(CH )sar](ClO
3
4
)
4
·2H
2
O (CoL3·(ClO
4
)
3
·HClO ·
4
H
35
N +
7
+
2H O). Excess CoCO (0.20 g, 1.7 mmol) was added to a solution
ClO
4
] . Anal. Calcd for CuC15
H
35.5
N
7
Cl2.5
O10: C, 28.77; H, 5.71;
2
3
of [(C10
H
21NH
2
)(CH
3
)sarH
4
]Cl (0.40 g, 0.63 mmol) in water (ca.
5
N, 15.66. Found C, 28.47; H, 5.13; N, 15.40. The compound was
converted to the acetate salt via passage through a column of
Dowex 1¥8 anion exchange resin (acetate form) and evaporating
the solution to dryness.
1
0 mL) and heated on a steam bath for 8 h, whilst bubbling air
through the mixture in order to oxidise the Co(II) to Co(III). The
mixture was then filtered, and the filtrate passed through a column
of Dowex 1¥8 anion exchange resin (acetate form) using MeOH as
the eluant. The solvent was then removed on the rotary evaporator,
and the orange residue dissolved in ca. 5 mL of MeOH, and cooled
[
Mg(NH
O). (NH
Mg(CH CO
2
)
2
sar](CH
sar·2H
·4H O (0.32 g, 1.5 mmol) were dissolved in
3
CO
2
)
2
·3.5H
2
O
(MgL2·(CH
3
CO
2
)
2
·3.5-
H
2
2
)
2
2
O
(L2) (0.50 g, 1.4 mmol) and
3
2
)
2
2
on ice before the addition of conc. HClO
yellow-orange precipitate. The solid was filtered and washed with
ice-cold water to give [Co(C10 )(CH )sar](ClO
·2H
CoL3·(ClO ·HClO ·2H O) (0.42g, 0.44mmol, 70%) as a yellow-
orange solid. The sample was recrystallised from hot MeOH. H
NMR (CD CN, 500 MHz): d 0.88 (t, 3H, -CH ), 0.91 (s, 3H,
cage–CH ), 1.25–1.40 (m, 14H, 7(–CH -)), 1.64 (apparent p, 2H,
CH -), 2.4–3.6 (m, 26 H, (-CH –N + cage–CH -), 5.61 (b, 3H,
cage–NH-), 5.80 (b, 3H, cage–NH-), 7.46 (b, 2H, - NH
NMR (CD CN, 125 MHz): d 14.38 (-CH ), 20.10 (cage–CH
3.36, 26.68, 26.84, 29.38, 29.94, 29.97, 30.12, 32.59 (tail–CH
3.13 (C of methyl cage cap), 45.11 (tail–CH
5.34, 55.62 (cage–CH -), 62.39 (C of amine cage cap). MS(ES)
, which produced a
4
EtOH (ca. 10 mL) and the solution was gently heated for 30 min,
with small portions of EtOH added periodically to maintain the
H
21NH
2
3
4
)
4
2
O
volume of solution. Et O was added to the warm solution until the
2
(
4
)
3
4
2
first traces of precipitate were observed, and the mixture cooled
1
◦
at -20 C overnight. The white solid thus obtained was collected,
3
3
washed with cold EtOH–Et
2
O (50/50 v/v) and Et
2
O to give
·3.5H O)
O, 300 MHz): d 1.91
-), 3.62 (m,
O, 75 MHz): d 23.95 (CH CO ),
-), 50.71 (cage C), 59.04 (cage–CH -). MS(ES)
] . Anal. Calcd for
7.5: C, 41.58; H, 9.11; N, 21.55. Found C, 41.52; H,
3
2
[
(
(
6
4
Mg(NH
2
)
2
sar](CH
3
CO
2
)
2
·3.5H
2
O
(MgL2·(CH
3
CO
2
)
2
2
-
2
2
2
1
0.49 g, 0.94 mmol, 67%). H NMR (D
s, 6H, 2(CH
H, cage–NH-). C NMR (D
9.97 (cage–CH
m/z): 397.29 [MgC14
2
+
13
2
-).
C
3
CO
2
)), 2.3–3.3 (m, 24H, cage–CH
2
),
3
3
3
1
3
2
3
2
2
4
5
-),
2
2
2
–N), 51.44, 55.27,
2
+
(
H
34
N
8
+ CH
3
CO
2
2
MgC18
H
47
N
8
O
+
(
m/z): 510.3694 [CoC25
H
55
N
7
- 2H] ; 610.1562 [CoC25
H
55
N -
7
8.72; N, 21.38.
+
2+
H + ClO
4
] ; 255.6242 [CoC25
H
55
N - H] . Anal. Calcd for
7
CoC25
H, 5.87; N, 10.11.
H
60
N
7
Cl
4
O18: C, 31.69; H, 6.38; N, 10.35. Found C, 31.31;
[
(C10
H
21NH
)(NH
2
)(CH
)sar](OAc)
20 mL) was added NaBH
3
)sarH
4
]Cl
5
(L3·5HCl). To a solution of
[
(
Mg(CH
3
2
2
(1.0 g, 2.2 mmol) in dry MeOH
CN (0.30 g, 4.8 mmol), causing some
3
[Cu(C10
H
21NH
2
)(CH
)(NH
(0.48 g, 3.0 mmol), acetic acid (0.3 mL) and NaBH
3.5 mmol) were dissolved in EtOH containing molecular sieves
3
)sar](ClO
4
)
3
·H
2
O (CuL3·(ClO
(1.0 g, 2.0 mmol), decanal
CN (0.22 g,
4
)
2
·HClO ·
4
effervescence. After 10 min, decanal (1.4 g, 8.8 mmol) was added,
causing more effervescence and the solution became noticeably
warm. The mixture was stirred at RT for 1.5 h, before conc. HCl
was added, causing vigorous effervescence and the precipitation of
a white solid. The solvent was removed on a rotary evaporator, and
the white solid obtained was extracted with n-hexane (3 ¥ 100 mL),
the organic extracts discarded, and the solid dissolved in 100 mL
H
2
O). [Cu(CH
3
2
)sar](CH CO
3
2 2
)
3
˚
(3 A, ca. 2 g) and the mixture stirred at RT for 15 min. After this
period, the mixture was decanted and conc. HCl added to the blue
solution, causing vigorous effervescence. The solvent was removed
on the rotary evaporator and the purple solid was suspended in
This journal is © The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 3433–3448 | 3443

View Article Online
H
2
O and extracted with CHCl
3
(4 ¥ 100 mL), and the organic
cation exchange resin. The column was washed successively with
extracts discarded. The aqueous fraction was concentrated on the
MeOH, H O, 1 M HCl(aq) and the ligand eluted with conc.
2
rotary evaporator, then the product was precipitated by the addi-
HCl/MeOH (50 : 50 v/v, 1 L). The solvent was removed on the
rotary evaporator, with regular addition of EtOH required in order
to suppress the extensive formation of foam in the apparatus.
The tacky clear solid obtained was then dissolved in dry MeOH
and precipitated by pouring into a rapidly stirred flask of dry
MeCN, giving a fine off-white powder which was collected under
tion of a saturated aqueous solution of NaClO , which was col-
4
lected and washed with ice-cold water. The solid thus obtained was
recrystallised from acetone/n-hexane, collected and then washed
with n-hexane to give [Cu(C10
CuL3·(ClO ·HClO ·H O) (1.06 g, 1.3 mmol, 65%) as a blue
powder. MS(ES) (m/z): 616.1 [CuC25 + ClO ]; 299.2
CN] . Anal. Calcd for CuC25 Cl
C, 35.97; H, 7.00; N, 11.75. Found C, 35.98; H, 6.25; N, 11.66.
H
21NH
2
)(CH
3
)sar](ClO
4
)
3
·H
2
O
(
4
)
2
4
2
H
55
N
7
4
N
2
on a Schlenk line and washed with more dry MeCN before
being dried under vacuum to give [(C14 )(CH )sarH ]Cl
(L5·7HCl) as an off white solid (0.90 g, 1.2 mmol, 55%). H NMR
O, 600 MHz): d 0.74 (t, 3H, -CH ), 0.89 (s, 3H, cage–CH ),
.10–1.24 (m, 20H, 10(-CH -)), 1.27 (apparent p, 2H, -CH -), 1.59
apparent p, 2H, -CH -), 3.02 (m, 2H, -CH -), 3.04–3.31 (m, 24
-). C NMR (D O, 150 MHz): d 14.19 (-CH ), 19.35
2
+
[CuC25
H
55
N
7
+ 2CH
3
H
58
N
7
3
O
13
:
H
29NH
2
3
6
7
1
(
D
2
3
3
[
Cu(C13
H
27NH
2
)(CH )sar](ClO (CuL4·(ClO ·HClO
)sar](CH CO (0.70 g, 1.4 mmol), tridecanal
0.48 g, 2.4 mmol) and acetic acid (0.25 mL) were dissolved in
3
4
)
3
4
)
2
4
).
1
(
2
2
[
(
Cu(CH
3
)(NH
2
3
)
2 2
2
2
1
3
H, cage–CH
2
2
3
◦
˚
EtOH (20 mL) at 55 C. Molecular sieves were added (3 A,
ca. 1 g) and the mixture stirred for 10 min before NaBH CN
0.16 g, 2.5 mmol) was added, producing some effervescence.
The reaction was allowed to continue for 30 min, TLC on silica
NH Cl/MeOH) indicating the reaction was complete, at which
time NaBH was added, followed 10 min later by conc. HCl,
(
3
4
cage–CH
3
), 22.82, 26.41, 26.78, 29.01, 29.29, 29.36, 29.50, 29.65,
2.01 (-CH -), 37.00 (C of methyl cage cap), 43.20 (-CH –N),
6.67, 48.32, 49.34, 54.17 (cage–CH -), 61.02 (C of amine cage
3
2
2
(
2
+
cap). MS(FAB) (m/z): 510.53 [C29
Cl
H
63
7
N + H] . Anal. Calcd for
(
4
C
29
H
70
N
7
7
: C, 45.53; H, 9.22; N, 12.82. Found C, 45.23; H, 9.10;
4
N, 12.21.
causing vigorous effervescence and a purple colour to appear in
solution. The mixture was filtered through Celite, and the filtrate
brought to dryness on the rotary evaporator. The purple residue
was suspended in MeOH, which was extracted with n-hexane (3 ¥
[Zn((C14
H
29NH
2
)(CH
3
)sar)](ClO
4
)
3
(ZnL5·(ClO
solution of
(0.40 g, 0.52 mmol) in water
4
)
2
·HClO
4
).
ZnO (0.16 g, 2.0 mmol) was added to
)(CH )sarH ]Cl
a
[(C14
H
29NH
2
3
6
7
5
0 mL), and the n-hexane extracts discarded. The MeOH solution
(ca. 20 mL) and the mixture heated on a steam bath for 8 h,
during which time water was added periodically to maintain
the volume of solution. The mixture was then filtered, and
the filtrate passed through a column of Dowex 1¥8 anion
exchange resin (acetate form). The solution was concentrated
on a rotary evaporator to a volume of ca. 20 mL before being
cooled on ice, and acidified by dropwise addition of conc.
was again brought to dryness on the rotary evaporator and the
residue dissolved in hot water, the solution filtered, and the product
precipitated by the dropwise addition of a saturated aqueous
solution of NaClO
water. Recrystallisation from hot MeCN by the addition of H
gave [Cu(C13 )(CH )sar](ClO
0.72 g, 0.84 mmol, 60%) as a blue opalescent solid. MS(ES)
4
, the solid collected and washed with ice-cold
2
O
H
27NH
2
3
4
)
3
(CuL4·(ClO
4
)
2
·HClO
4
)
(
HClO
The solid was filtered and washed with ice-cold water to give
)(CH )sar](ClO ) (0.42 g,
4
(ca. 3 mL), producing a white precipitate immediately.
+
(
m/z): 657.2 [CuC28
H
61
N
H
7
+ ClO
4
] ; 299.7 [CuC28
H
61
N
7
+
2
+
2+
CH
CuC28
3
CN] ; 320.3 [CuC28
Cl
61
N
7
+ 2CH
3
CN] . Anal. Calcd for
[Zn(C14
H
29NH
2
3
4
)
3
(ZnL5·(ClO
4
)
2
·HClO
4
H
62
N
7
3
O
12: C, 39.16; H, 7.28; N, 11.42. Found C, 39.17;
0.48 mmol, 92%) as a white powder. The sample was recrystallised
H, 7.34; N, 11.10. Crystals suitable for the X-ray work were
grown using two methods. Method 1 involved the slow deposition
of crystals from a hot dilute aqueous solution of the complex
in a branched tube flask, the structure solution indicating a
from hot water, giving a white opalescent semi-crystalline solid.
1
H NMR (CD
), 1.20–1.40 (m, 22H, 11(-CH
-), 2.40–3.60 (m, 32H, (-CH –N + cage–NH- + cage–CH
3
CN, 500 MHz): 0.64 (s, 3H, cage–CH
3
), 0.88 (t,
3H, -CH
-CH
6.95 (br, 1H, - N(H)H-(CH
3
2
-)), 1.60 (apparent p, 2H,
2
2
2
-)),
+
+
composition of CuL4·(ClO
except for the addition of a few drops of conc. HClO
aqueous solution; in this case, the structure solution indicating a
composition of CuL4·(ClO ·HClO ·2H O (i.e. CuHL4).
4
)
2
. Method 2 was identical to Method
2
)
n
-), 7.05 (br, 1H, - N(H)H-(CH
2
)
n
-).
-),
1
3
1
4
to the
C NMR (CD
3
CN, 125 MHz): 14.39 (-CH
3
), 23.39 (-CH
2
24.31 (cage–CH
30.36, 30.38, 30.40, 32.64 (-CH
4
3
), 26.84, 27.04, 29.51, 29.99, 30.07, 30.20, 30.33,
-), 34.76 (C of methyl cage cap),
3.47, 49.36, 49.62, 53.48 (cage -CH -), 57.93 (C of amine cage
4
)
2
4
2
2
2
[
(C14
H
29NH
)(CH
2
)(CH )sarH ]Cl (L5·7HCl). To a solution of
)sar](OAc) (1.0 g, 2.2 mmol) in dry MeOH
20 mL) was added NaBH CN (0.30 g, 4.8 mmol), causing
3
6
7
cap), 59.05 (cage–CH
2
-). MS(ES) (m/z): 672.38 [ZnC29
H
H
63
N
7
+
+
[
(
Mg(NH
2
3
2
+
2+
ClO
CH
.38; N, 11.21. Found C, 39.82; H, 6.85; N, 10.75. Crystals
4
] ; 327.69 [ZnC29
CN] . Anal. Calcd for ZnC29
H
63
N
7
+ 2CH
3
CN] ; 307.10 [ZnC29
63
N
7
3
2
+
3
H
64
N
7
3
Cl O12: C, 39.82; H,
some effervescence. After 10 min, tetradecanal (2.33 g, 11 mmol)
in CHCl (15 mL) was added to the solution, causing some
7
3
suitable for the X-ray work were grown by slow cooling of a hot
aqueous solution of the complex, indicating a composition of
effervescence and warming of the solution. The mixture was stirred
for 12 h before conc. HCl (ca. 20 mL) was added, causing vigorous
effervescence and the precipitation of a white solid. The mixture
was brought to dryness on the rotary evaporator, and the white
solid thus obtained was extracted with n-hexane (3 ¥ 100 mL)
before conc. HCl/MeOH (50 : 50 v/v, ca. 250 mL) was added and
ZnL5·(ClO
[Co((C14
HClO O). CoCO
·H
solution of [(C14
in water (ca. 10 mL) and the mixture heated at 50 C for
8 h whilst a stream of air was bubbled through the solution.
The workup procedure was identical to that described above
4
)
2
.
H
29NH
2
)(CH
3
)sar)](ClO
(0.075 g, 0.63 mmol) was added to a
4
)
4
·H
2
O
(CoL5·(ClO
4
)
3
·
4
2
3
H
29NH
2
)(CH
3
)sarH
6
]Cl
7
(0.30 g, 0.39 mmol)
◦
◦
the mixture heated at 70 C for 8 h, causing most of the initially
insoluble white material to dissolve within ca. 1 h. The solvent
was then removed on the rotary evaporator, and the white solid
+
dissolved in MeOH and applied to a column of H Dowex 50W¥2
for ZnL5 to give [Co((C14
H
29NH
2
)(CH
3
)sar)](ClO
4
)
4
·H
2
O
3
444 | Dalton Trans., 2010, 39, 3433–3448
This journal is © The Royal Society of Chemistry 2010

View Article Online
(
CoL5·(ClO
4
)
3
·HClO
4
·H
2
O) (0.28 g, 0.28 mmol, 72%) as an
24 h. Concentrated HCl was then added (ca. 20 mL) producing
vigorous effervescence and a white precipitate, and the solvent
was removed on a rotary evaporator. The white solid thus
orange waxy solid. The sample was recrystallised from hot water.
1
H NMR (CD CN, 600 MHz): d 0.88 (t, 3H, -CH
3
3
), 0.91 (s, 3H,
cage–CH ), 1.22–1.37 (br, 22 H, 11(-CH -)), 1.61 (apparent p,
-), 2.4–3.6 (m, 26 H, (-CH –N + cage–CH -)), 5.60 (br,
H, cage–NH-), 5.77 (br, 3H, cage–NH-). C NMR (CD CN,
50 MHz): d 14.39 (-CH ), 20.11 (cage–CH ), 23.38, 26.80,
7.29, 29.48, 30.00, 30.06, 30.21, 30.33, 30.35, 30.38, 30.39,
2.63 (-CH -), 43.12 (C of methyl cage cap), 44.85 (-CH –N),
1.78, 55.32, 55.37, 55.65 (cage–CH
3
2
obtained was extracted with CHCl (3 ¥ 100 mL), the organic
3
2
3
1
2
3
5
H, -CH
2
2
2
layers decanted and discarded, and the remaining solid dissolved
in MeOH/conc. HCl (50 : 50 v/v), the solution heated at reflux
for 5 h, then brought to dryness on the rotary evaporator.
The white solid thus obtained was dissolved in MeOH and
applied to a column of Dowex 50W¥2 cation exchange resin,
1
3
3
3
3
2
2
2
-), 62.31 (C of amino cage
washed with H O, 1M HCl (500 mL each), and finally the
2
+
cap). MS(ES) (m/z): 766.46 [CoC29
H
63
N
7
+ 2ClO
4
] ; 283.78
ligand was eluted from the column with a mixture of conc.
HCl/MeOH (50 : 50 v/v, 500 mL). The solvent from this fraction
was removed on the rotary evaporator, the white solid thus
obtained dissolved in MeOH, cooled on ice, and the ligand
2
+
2+
[CoC29
H
63
N
7
- H] ; 304.29 [CoC29
H
63
N
7
- H + CH
CN] ; 666.49 [CoC29
Cl 17: C, 35.34; H, 6.75; N,
3
CN] ;
2
+
3
ClO
24.79 [CoC29
H
63
N
7
- H + 2CH
3
H
63
7
N –H +
+
4
] . Anal. Calcd for CoC29
H
66
N
7
4
O
9
.95. Found C, 35.49; H, 6.93; N, 9.76.
precipitated by the addition of 4M HNO
freezer. The precipitate was collected by suction filtration to give
(C sarH ](NO ) (2.2 g, 2.9 mmol, 66%)
(L6·4HNO
as a white solid. The sample was recrystallised from hot H
NMR (d -DMSO, 300 MHz): d 0.85 (t, 6H, 2(-CH )), 1.25 (m, 16
H, 8(-CH -)), 1.52 (m, 4H, 2(-CH -)), 2.85 (br s, 16 H, (2(-CH -) +
cage–CH -))), 3.15 (br s, 12H, (cage–CH -)), 5.5–7.5 (br, 6H,
cage–NH-). C NMR (d -DMSO, 75 MHz): d 13.95 (-CH ),
1.96, 25.96, 26.48, 28.14, 31.08, 41.11 (-CH -), 47.26, 51.42
3
(aq) and cooling in the
[
Cu(C14
H
29NH
2
)(CH )sar](ClO
3
4
)
3
·H
2
O (CuL5·(ClO
4
)
2
·HClO ·
4
[
7
H
15NH
2
)
2
2
3
)
4
3
H
2
O).
1
2
O. H
Method A. [Cu(CH
3
)(NH
2
)sar](OAc)
2
(1.0 g, 2.0 mmol),
6
3
tetradecanal (0.66 g, 3.1 mmol), and acetic acid (0.3 mL)
were dissolved in EtOH (50 mL) which contained molecular
2
2
2
(
2
2
◦
˚
sieves (3 A, ca. 2 g) and the mixture stirred at 60 C. After
5 min, the reaction was quenched with HCl and the prod-
uct isolated in an analogous manner to that described for
compound CuL4 to give [Cu(C14 )(CH )sar](ClO
·H
O) (1.3 g, 1.5 mmol, 75%) as a blue
13
6
3
1
2
2
(
cage-CH
2
-), 55.90 (cage C). MS(ES) (m/z): 511.52 [C28
H
N
62
N
8
+
H
29NH
2
3
4
)
3
2
O
+
2+
H] ; 256.26 [C28
H
62
N
8
+ 2H] . Anal. Calcd for C28
H
66
12
O :
12
(
CuL5·(ClO
4
)
2
·HClO
4
·H
2
C, 44.08; H, 8.72; N, 22.03. Found C, 44.00; H, 8.52; N,
1.86.
opalescent solid.
2
Method B. CuCO
3
·Cu(OH)
2
(0.05 g, 0.23 mmol) was added to
)sarH ]Cl (0.062 g, 0.081 mmol)
[
Co(C
HClO
·3H
was added to a hot aqueous solution (ca. 20 mL) of
(C sarH ](NO (0.40 g, 0.53 mmol), producing
7
H
15NH)(C
O). Co(CH
7
H
15NH
2
)sar](ClO
4
)
4
·3H
2
O
(CoL6·(ClO
4
)
3
·
a solution of [(C14
H
29NH
2
)(CH
3
6
7
4
2
3
CO
2
)
2
·4H
2
O (0.40 g, 1.6 mmol)
in water (ca. 10 mL) causing immediate effervescence and a deep
blue colour to appear in solution. The mixture was heated on the
steam bath for ca. 4 h, and the workup procedure conducted as
[
7
H
15NH
2
)
2
2
)
3 4
a deep pink solution, which was heated on the steam bath for 5 h.
Compressed air was periodically bubbled through the solution to
ensure it was fully oxygenated, producing a deep orange solution
within 1 h. After the heating step, the solution was slurried with
Dowex 1¥8 anion exchange resin (acetate form) for 30 min before
the slurry was loaded onto a column of the same material, and
the orange solution eluted with water. The solvent was removed
on the rotary evaporator to give a pink-orange solid which was
slurried in EtOH and cooled on ice. To this mixture was added
4
described for ZnL5 to give [Cu(C14
CuL5·(ClO ·HClO ·H O) (0.039 g, 0.044 mmol, 54%) as a waxy
blue solid. The sample was recrystallised from hot water. MS(ES)
H
29NH
2
)(CH
3
)sar](ClO
4
)
3
·H
2
O
(
4
)
2
4
2
+
(
m/z): 671.45 [CuC29
H
63
N
H
7
+ ClO
4
] ; 306.77 [CuC29
H
63
N +
7
2
+
2+
CH
3
CN] ; 327.29 [CuC29
Cl
H, 7.43; N, 10.75.
63
N
7
+ 2CH CN] . Anal. Calcd for
3
CuC29
H
66
N
7
3
O13: C, 39.10; H, 7.47; N, 11.01. Found C, 39.29;
[
Ni(C14
H
29NH
2
)(CH
(0.02 g, 0.2 mmol) was added to a solution of
)(CH )sarH ]Cl (0.066 g, 0.086 mmol) in water (ca.
0 mL), producing some effervescence. The mixture was heated
3
)sar](ClO
4
)
3
·H
2
O (NiL5·(ClO
4
)
2
·HClO
4
·
H
[
1
2
O). NiCO
3
conc. HClO , causing the precipitation of the complex, which
(C14
H
29NH
2
3
6
7
was collected and washed with cold EtOH and Et O to give
2
[Co(C H NH) sar](ClO ) ·3H O (CoL6·(ClO ) ·HClO ·3H O)
7
15
2
4
4
2
4
3
4
2
on the steam bath for ca. 8 h, at which time the peach coloured
solution was filtered and the workup procedure conducted as
(0.36 g, 0.35 mmol, 66%) as a waxy orange powder. The sample
was recrystallised from warm MeCN by the addition of EtOH
1
described for ZnL5 to give [Ni(C14
NiL5·(ClO ·HClO ·H O) (0.044 g, 0.050 mmol, 58%) as a
pale pink waxy solid. The sample was recrystallised from hot
H
29NH
2
)(CH
3
)sar](ClO
4
)
3
·H
2
O
and allowed to cool to room temperature. H NMR (CD CN,
3
(
4
)
2
4
2
300 MHz): d 0.90 (t, 6H, 2(-CH )), 1.20–1.45 (m, 16H, 8(-CH -)),
3
2
1.62 (apparent p, 4H, 2(-CH -)), 2.85–3.15 (m, 28H, (2(-CH –
2
2
+
13
water. MS(ES) (m/z): 666.47 [NiC29
H
63
N
H
7
+ ClO
+ 2CH
13: C, 39.32; H, 7.51; N, 11.07.
Found C, 39.52; H, 7.41; N, 10.83.
4
] ; 304.28
N) + cage–CH -), 6.37 (br, 6H, cage–NH-). C NMR (CD CN,
2
3
2
+
2+
[NiC29
H
63
N
7
+ CH
3
CN] ; 324.79 [NiC29
Cl
63
N
7
3
CN] .
75 MHz): d 14.32 (-CH ), 23.19, 26.80, 27.33, 29.17, 32.18, 44.69
3
Anal. Calcd for NiC29
H
66
N
7
3
O
(-CH -), 51.11, 54.22 (cage -CH -), 62.15 (cage C). MS(ES) (m/z):
2
2
2
+
+
284.21 [CoC H N - H] ; 767.34 [CoC H N + 2ClO ] . Anal.
2
8
62
8
28
62
8
4
Calcd for CoC28
C, 32.46; H, 6.38; N, 10.90.
H
69
N
8
Cl O19: C, 32.89; H, 6.80; N, 10.96. Found
4
[
(C sarH ](NO (L6·4HNO
7
H
15NH
2
)
2
2
3
)
4
3
). [Mg(NH ) sar]-
2
2
(
OAc) O (MgL2) (2.0 g, 4.4 mmol) was dissolved in dry
MeOH (30 mL) in a round bottomed flask, and to this was
added NaBH CN (1.1 g, 18 mmol) producing some effervescence.
After 10 min, heptanal (4.0 g, 35 mmol) was added to the
solution and the flask was stoppered and left to stand at RT for
2
·3.5H
2
[Zn(C sar](ClO
2H O). An excess of ZnO (0.14 g, 1.7 mmol) was added to a
hot aqueous solution (ca. 10 mL) of [(C sarH ](NO
7
H
15NH
2
)
2
4
)
4
·2H
2
O
(ZnL6·(ClO
4
)
2
·2HClO ·
4
3
2
7
H
15NH
2
)
2
2
)
3 4
(0.50 g, 0.66 mmol) and the mixture heated on the steam bath for
This journal is © The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 3433–3448 | 3445

View Article Online
6
h. The mixture was then filtered, and the filtrate diluted with
conc. HCl (ca. 10 mL) was added, causing vigorous effervescence.
The solvents were removed on the rotary evaporator, the thick
white slurry extracted with n-hexane (5 ¥ 100 mL), and the
organic extracts discarded. The white solid was then suspended
in EtOH/conc. HCl (500 mL, 50 : 50 v/v) before being heated
at reflux for 12 h, during which time most of the white solid
dissolved. After this period, the solvent was removed on the
rotary evaporator, and the white solid dissolved in MeOH and
water (ca. 100 mL) and passed through a column of Dowex 1¥8
anion exchange resin (acetate form) using water as the eluant.
The solution was brought to dryness on a rotary evaporator, and
the white residue was dissolved in EtOH, which was cooled on ice
before the addition of a saturated aqueous solution of NaClO
mL) followed by dropwise addition of conc. HClO , producing a
white precipitate immediately. Addition of HClO was continued
4
(ca.
5
4
4
+
until no further precipitation was observed (ca. 1 mL), and
the mixture was cooled at -20 C before being filtered and
applied to a column of H Dowex 50W¥2 cation exchange
◦
resin. The column was washed with MeOH, H O, and 1 M
2
washed with cold EtOH to give [Zn(C
ZnL6·(ClO ·2HClO ·2H O) (0.60 g, 0.59 mmol, 89%) as a
white opalescent solid. The sample was recrystallised from hot
7
H
15NH
2
)
2
sar](ClO
4
)
4
·2H
2
O
HCl (500 mL each). Elution with MeOH or EtOH/conc. HCl
(50 : 50 v/v) proved to elute the product very slowly from the
column, owing to the low solubility of the ligand in this solvent
mixture at RT, and thus the resin was placed into a large conical
flask, and stirred in MeOH/conc. HCl (1 L, 50 : 50 v/v) heated
(
4
)
2
4
2
◦
1
MeCN by the addition of EtOH and cooling at -20 C. H NMR
CD CN, 300 MHz): d 0.89 (t, 6H, 2(-CH )), 1.20–1.40 (m, 16H,
(-CH -)), 1.59 (apparent p, 4H, 2(-CH -)), 2.45–3.65 (m, 32H,
2(-CH –N) + cage–CH - + cage–NH-)). C NMR (CD
5 MHz): d 14.30 (-CH ), 23.18, 26.76, 26.97, 29.14, 32.14, 43.44
-), 49.21, 53.24 (cage -CH -), 57.59 (cage C). MS(ES) (m/z):
(
3
3
◦
8
(
2
2
to 50–60 C on a heater-stirrer. After filtration, the solvent was
1
3
2
2
3
CN,
removed on the rotary evaporator to give an off-white solid,
which was recrystallised by dissolving in hot MeOH, filtering
7
3
◦
(
2
-CH
87.22 [ZnC28
2
2
and allowing to cool to RT before being stored at -20 C for a
2
+
+
H
62
N
8
] ; 673.38 [ZnC28
H
62
N
8
+ ClO
4
] . Anal.
few hours to give [(C14
(1.62 g, 1.8 mmol, 58%) as an off-white powder. H NMR
H
29NH
2
)
2
sarH
2
]Cl
4
·2H
2
O (L7·4HCl·2H
2
O)
1
Calcd for ZnC28
H
68
N
8
Cl 18: C, 33.23; H, 6.77; N, 11.07. Found
4
O
C, 33.37; H, 6.27; N, 10.77.
(CD
3
OD, 600 MHz): d 0.90 (t, 6H, 2(-CH
4H, 22(-CH -)), 1.70 (apparent p, 4H, 2(-CH
H, 2(-CH –N)), 3.13 (br s, 12 H, 6(cage–CH -)), 3.42 (br s,
H, 6(cage–CH OD, 150 MHz): d 14.43
), 23.72, 27.57, 27.94, 30.19, 30.46, 30.50, 30.62, 30.73,
0.75, 30.76, 30.78, 33.06, 43.23 (-CH -), 48.78, 52.88 (cage–
-), 57.93 (cage C). MS(FAB) (m/z): 707.21 [C42 N +
3
)), 1.25–1.45 (m,
4
4
4
2
2
-)), 3.06 (m,
[
Ni(C sar](ClO
7
H
15NH
2
)
2
4
)
4
·2H
2
O
(NiL6·(ClO
4
)
2
·2HClO ·
4
2
2
2
H
2
O). NiCO (0.02 g, 0.17 mmol) was added to a solution
3
2
13
2
-)). C NMR (CD
3
of [(C sarH ](NO (0.05 g, 0.07 mmol) in water (ca.
7
H
15NH
2
)
2
)
3 4
(
-CH
3
1
0 mL) and the mixture heated on the steam bath for 8 h giving
3
2
a peach coloured solution. The mixture was filtered, and the
filtrate passed through a column of Dowex 1¥8 anion exchange
resin (acetate form) using water as the eluant. The eluate was
reduced to dryness on the rotary evaporator before the residue
was dissolved in MeOH, the solution cooled on ice, and conc.
CH
2
H
90
8
+
H] . Anal. Calcd for C42
H
98
N
8
Cl
4
O
2
: C, 56.74; H, 11.11; N,
1
2.60. Found C, 56.59; H, 10.92; N, 12.28. Crystals suitable for
the X-ray work were grown by slow evaporation of a MeOH
solution of the ligand. The structure solution was modelled as
HClO
solid which was collected and washed with ice cold MeOH to give
Ni(C sar](ClO O (NiL6·(ClO ·2HClO ·2H O)
·2H
0.046 g, 0.046 mmol, 66%) as a waxy pink solid. The sample
4
added dropwise causing the immediate precipitation of a
[
(C14
H
29NH
2
)
2
sarH
2
]Cl
4
·2H
2
O·2CH
3
OH.
[
7
H
15NH
2
)
2
4
)
4
2
4
)
2
4
2
[
Zn(C14
H
29NH
2
)
2
sar](ClO
4
)
4
·4H
2
O
(ZnL7·(ClO
4
)
2
·2HClO ·
4
(
4H
2
O). ZnO (0.06 g, 0.7 mmol) was added to a solution of
sarH ]Cl O (0.30 g, 0.34 mmol) in MeOH
·2H
ca. 20 mL) and the mixture heated at reflux for 8 h causing
a white precipitate to form. The mixture was diluted to ca.
00 mL by the addition of MeOH, filtered and the filtrate
passed through a column of Dowex 1¥8 anion exchange resin
acetate form), which was washed with further MeOH. The
was recrystallised from hot water. MS(ES) (m/z): 667.40
[
(C14
H
29NH
2
)
2
2
4
2
+
2+
[
NiC28
H
62
N
8
+ ClO
Cl
H, 6.89; N, 10.92.
4
] ; 284.22 [NiC28
H
62
N ] . Anal. Calcd for
8
(
NiC28
H
68
N
8
4
O18: C, 33.45; H, 6.82; N, 11.15. Found C, 33.31;
2
[
Cu(C
CuCO
·Cu(OH)
(C
mL) and the mixture heated on the steam bath for ca. 2 h, to
give a deep blue solution. The workup procedure was identical to
that described for NiL6 to give [Cu(C sar](ClO
·6H
CuL6·(ClO ·2HClO ·6H O) (0.042 g, 0.04 mmol, 57%) as
a waxy blue solid. The sample was recrystallised from hot
7
H
15NH
2
)
2
sar](ClO
(0.03 g, 0.14 mmol) was added to a solution of
]·(NO (0.05 g, 0.07 mmol) in hot H O (ca.
4
)
4
(CuL6·(ClO
4
)
2
·2HClO
4
·6H
2
O).
(
3
2
eluate was concentrated on the rotary evaporator to a volume
of ca. 10 mL, cooled on ice and the complex precipitated by
[
5
7
H
15NH
2
)
2
sarH
2
3
)
4
2
the addition of conc. HClO
with cold water to give [Zn(C14
O) (0.39 g, 0.31 mmol, 91%) as a
4
. The solid was filtered and washed
sar](ClO
·4H
2
H
29NH
2
)
2
4
)
4
2
O
7
H
15NH
2
)
2
4
)
4
2
O
(
ZnL7·(ClO
4
)
2
·2HClO
4
·4H
(
4
)
2
4
2
white opalescent waxy solid. The sample was recrystallised from
1
+
MeCN by the addition of MeOH and cooling on ice. H NMR
water. MS(ES) (m/z): 672.39 [CuC28
H
62
N
8
+ ClO
Cl 22: C, 31.07; H,
.08; N, 10.35. Found C, 31.19; H, 6.58; N, 9.81.
4
] ; 286.72
2
+
(CD
3
CN, 500 MHz): d 0.88 (t, 6H, 2(-CH
4H, 22(-CH -)), 1.60 (apparent p, 4H, 2(-CH
0H, (cage–CH - + cage–NH-)), 2.89 (m, 2H, 2(-C(H)H–N)),
3
)), 1.20–1.40 (m,
[
7
CuC28
H
62
N
8
] . Anal. Calcd for CuC28
H
76
N
8
4
O
4
3
2
2
-)), 2.55–3.60 (m,
2
1
3
[
(C14
H
29NH
2
)
2
sarH
CO
dry MeOH (25 mL), and to this solution was added NaBH
0.85 g, 13 mmol), causing some effervescence. After 10 min,
tetradecanal (5.30 g, 25 mmol) was added to the solution, and
CHCl added to the mixture until all of the solid had dissolved
ca. 10 mL). This mixture was stirred for 15 h, after which time
2
]Cl
·3.5H
4
·2H
O (1.42 g, 3.1 mmol) was dissolved in
CN
2
O
(L7·4HCl·2H
2
O). [Mg-
3.09 (m, 2H, 2(-C(H)H–N)). C NMR (CD
d 14.39 (-CH ), 23.39, 26.84, 27.00, 29.50, 29.99, 30.07, 30.21,
30.33, 30.36, 30.38, 30.40, 32.64 (-CH -), 43.54 (-CH –N),
49.26, 53.27 (cage–CH -), 57.73 (C). MS(ES) (m/z): 405.7825
[ZnC42
for ZnC42
3
CN, 125 MHz):
(
NH
2
)
2
sar](CH
3
2
)
2
2
3
3
2
2
(
2
2
+
2+
H
90
N
H
8
+ CH
Cl
3
CN] ; 385.3299 [ZnC42
O
H
90
N ] . Anal. Calcd
8
3
100
N
8
4
20: C, 40.54; H, 8.10; N, 9.00. Found C,
(
40.67; H, 7.69; N, 8.76.
3
446 | Dalton Trans., 2010, 39, 3433–3448
This journal is © The Royal Society of Chemistry 2010

View Article Online
Table 1 Selected X-ray data collection and refinement data for the ligands and complexes
L1·4HCl·7/3H
2
O
L7· 4HCl·2H
2
O·2CH
3
OH
CuL4·(ClO
4
)
2
Cu(HL4)·(ClO
CuN
4
)
2
·HClO
4
·2H
2
O
ZnL5·(ClO
4 2
)
Empirical formula
Formula weight
T/K
C
15
H
43.67Cl
4
N
7
O
2.33
C
44
H
106Cl
4
N
8
O
4
C
28
H
61Cl
2
CuN
7
O
8
C
28
H
66Cl
3
7
O
14
29 2 7 8
C H63Cl N O Zn
501.37
150(2)
0.71073
953.17
100(2)
0.71073
758.28
100(2)
1.54178
Triclinic
¯
P1
8.803(3)
17.759(4)
27.012(10)
91.86(2)
99.60(2)
119.65(2)
3586(2)
4
1.405
2.694
1620
894.77
100(2)
0.76600
Triclinic
¯
P1
8.5910(10)
8.6340(10)
31.316(5)
95.803(10)
91.411(10)
119.620(10)
2001.5(5)
2
1.485
0.816
950
0.25 ¥ 0.10 ¥ 0.08
2.12–27.50
0.83
774.13
110(2)
0.49594
Triclinic
¯
P1
8.7770(10)
8.8680(10)
27.515(3)
93.830(3)
94.964(3)
117.163(3)
1884.6(4)
2
1.364
0.848
828
0.11 ¥ 0.09 ¥ 0.06
4.06–17.18
0.84
Wavelength/A˚
Crystal system
Monoclinic
Monoclinic
Space group
P2 /c
1
P2 /c
1
a/A˚
20.116(5)
16.196(4)
45.918(11)
90
99.887(3)
90
14738(6)
24
1.356
0.509
6464
0.28 ¥ 0.27 ¥ 0.17
0.90–25.87
0.81
9.3572(3)
14.2614(5)
42.0780(10)
90
96.001(3)
90
5584.4(3)
4
1.134
0.256
2104
0.19 ¥ 0.17 ¥ 0.03
2.49–25.00
0.84
b/A˚
c/A˚
◦
a ( )
◦
◦
b ( )
◦
g ( )
V/A˚
3
Z
c
-3
r
/g cm
-1
m/mm
F(000)
Crystal size/mm
0.28 ¥ 0.16 ¥ 0.13
2.89–66.04
0.84
◦
q range ( )
Resolution dmax ( A˚ )
Reflections collected
93467
47180
38793
29344
28352
Ind. reflections [Rint
]
25982 [0.049]
Multi-scan
1.00/0.84
9783 [0.149]
Multi-scan
0.99/0.83
9783/8/564
0.896
0.0747, 0.1389
0.1965, 0.1618
1.047, -0.484
12163 [0.043]
Multi-scan
0.70/0.40
12163/488/788
1.892
0.1840, 0.3883
0.2142, 0.4259
2.864, -0.613
6666 [0.084]
Sphere
0.95/0.92
6666/20/569
1.043
0.0908, 0.2458
0.0917, 0.2467
1.175, -0.855
6365 [0.043]
None
—
6365/225/467
1.047
0.1170, 0.3430
0.1278, 0.3452
2.037, -1.431
Abs. correction
Max./min. trans.
Data/restr./paramet. 25982/18/1636
2
GOF on F
1.120
R
R
1
, wR
, wR
2
[I > 2s(I)]
0.0847, 0.2005
0.1129, 0.2125
1.602, -1.054
1
2
(all data)
Largest diff. peak
and hole e A˚
-3
[
H
(C14
Co(C14
H
29NH)
2
sar]Cl
O (0.075 g, 0.30 mmol) was added to a solution of
sarH ]Cl O (0.20 g, 0.23 mmol) in MeOH (ca.
·2H
0 mL), causing a rapid colour change in solution to a deep
3
·2H
2
O (CoL7·Cl
3
·2H
2
O). Co(OAc)
2
·
CuL4 were collected on an Oxford Diffraction Gemini diffrac-
tometer with Cu-Ka radiation. Data for Cu(HL4) and ZnL5 were
4
[
2
2
H
29NH
2
)
2
2
4
2
collected on synchrotrons. The structures were refined against
2
F
with full-matrix least-squares using the program SHELXL-
◦
34
orange-brown colour. The solution was heated at 50 C for 5 h
whilst air was gently bubbled through the solution continuously.
After this time, the solution was allowed to cool to RT before the
flask was placed in an ice bath as an orange precipitate began to
form. The solid was collected on a sintered glass frit and washed
with ice cold MeOH and water. The sample was dissolved in hot
MeOH, filtered and recrystallised by cooling to RT and finally
in an ice bath, then filtered and washed with ice cold MeOH
97. Except where stated, anisotropic displacement factors were
employed throughout for the non-hydrogen atoms with H atoms
added at calculated positions and refined by use of a riding
model with isotropic displacement parameters based on that of
the parent atom. Pertinent details are given in Table 1 and Fig. 1–
5 where the ellipsoids are drawn at the 30% probability level for
CuL4 and ZnCl5 and at the 50% level for the remainder. For L1,
assignments of the NH
3
and NH groups were made on the basis
2
and dried under vacuum to give [Co(C14
CoL7·Cl ·2H O) (0.11 g, 0.12 mmol, 52%) as an orange semi-
crystalline solid. H NMR (d
(-CH )), 1.18–1.30 (br, 48H, 24(-CH
), 2.30–3.05 (m, 26 H, (2(-CH –N) + cage–CH
-DMSO, 150 MHz): d 13.95 (-CH
2.08, 26.63, 28.69, 28.92, 29.00, 29.01, 29.04, 29.05, 29.06, 30.48,
1.28 (-CH -), 40.99 (-CH –N), 52.13, 54.32 (cage–CH -), 60.76
–H + Cl] . Anal. Calcd for
: C, 55.52; H, 10.43; N, 12.33. Found C, 55.89;
H, 10.20; N, 12.16.
H
29NH)
2
sar]Cl
3
·2H
2
O
of refinement and H-bonding considerations. The O atoms of the
perchlorate anions were modeled as being disordered over two
(
3
2
1
6
-DMSO, 600 MHz): d 0.85 (t, 6H,
sets of sites with occupancy factors set to 0.5 (for ClO
trial refinement and 0.816(5) and its complement for ClO
4
(1)) after
(2). For
2
)
3
2
-)), 1.87 (m, 2H, 2(-NH-
-)), 8.18 (br, 6H,
),
4
2
2
L7, the solvent was modeled as two water molecules and two
MeOH molecules. One MeOH was disordered over two sites with
occupancyfactors refinedto0.692(7)andits complement. Hatoms
1
3
cage–NH-). C NMR (d
2
3
6
3
2
2
2
for one H
2
O and for the MeOH molecules were not included. For
28N chains and of
+
(
C). MS(ES) (m/z): 799.69 [CoC42
Cl
H
90
N
8
CuL4, the geometries of the C atoms of the C13H
CoC42
H
94
N
8
3
O
2
the perchlorate anions were restrained to ideal values. For CuL4,
Cu(HL4) and ZnL5, the coordinating N atoms were modeled as
being disordered over two sets of sites with occupancy factors
set at 0.5 with these being refined with isotropic displacement
parameters only for CuL4. For Cu(HL4), the O atoms of the
perchlorate anions (2) and (3) were modeled as being disordered
over two sets of sites with occupancy factors of 0.878(5) and its
complement and with geometries restrained to ideal values. For
Crystal structural determinations
Crystallographic data for ZnL5 and L7 were collected on Bruker
Smart and Oxford Diffraction Xcalibur diffractometers respec-
tively with graphite-monochromated Mo-Ka radiation. Data for
This journal is © The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 3433–3448 | 3447

View Article Online
ZnL5 the O atoms of both perchlorate anions were modeled as
being disordered over two sets of sites with occupancy factors set
to 0.5 after trial refinement. Geometries were again restrained to
ideal values.
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Acknowledgements
GLN was the holder of an Australian Postgraduate Award.
Data for Cu(HL4) were collected on the PX1 beamline at the
Australian Synchrotron, Victoria, Australia. The views expressed
herein are those of the authors and are not necessarily those
of the owner or operator of the Australian Synchrotron. Use
of the ChemMatCARS Sector 15 at the Advanced Photon
Source, for ZnL5, was supported by the Australian Synchrotron
Research Program, which is funded by the Commonwealth of
Australia under the Major National Research Facilities Program.
ChemMatCARS Sector 15 is also supported by the National
Science Foundation/Department of Energy under grant numbers
CHE9522232 and CHE0087817 and by the Illinois board of higher
education. The Advanced Photon Source is supported by the U.S.
Department of Energy, Basic Energy Sciences, Office of Science,
under Contract No. W-31-109-Eng-38.
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3
448 | Dalton Trans., 2010, 39, 3433–3448
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