Interaction between anions and cationic metal complexes containing tridentate ligands with exo-C-H groups: Complex stability and hydrogen bonding

Article abstract of DOI:10.1002/chem.201303653

[Re(CO)₃([9]aneS₃)][BAr′₄] (1), prepared by reaction of ReBr(CO)₅, 1,4,7-trithiacyclononane ([9]aneS₃) and NaBAr′₄, forms stable, soluble supramolecular adducts with chloride (2), bromide, methanosulfonate (3) and fluoride (4) anions. These new species were characterized by IR, NMR spectroscopy and, for 2 and 3, also by X-ray diffraction. The results of the solid state structure determinations indicate the formation of CH X hydrogen bonds between the anion (X) and the exo-C-H groups of the [9]aneS₃ ligand, in accord with the relatively large shifts found by ¹HNMR spectroscopy in dichloromethane solution for those hydrogens. The stability of the chloride adduct contrasts with the lability of the [9]aneS₃ ligand in allyldicarbonyl molybdenum complexes recently studied by us. With fluoride, in dichloromethane solution, a second, minor neutral dimeric species 5 is formed in addition to 4. In 4, the deprotonation of a C-H group of the [9]aneS₃ ligand, accompanied by C-S bond cleavage and dimerization, afforded 5, featuring bridging thiolates. Compounds [Mo(η³- methallyl)(CO)₂(TpyN)][BAr′₄] (6) and [Mo(η³-methallyl)(CO)₂(TpyCH)][BAr′₄] (7) were synthesized by the reactions of [MoCl(η³-methallyl)(CO) ₂(NCMe)₂], NaBAr′₄ and tris(2-pyridyl)amine (TpyN) or tris(2-pyridyl)methane (TpyCH) respectively, and characterized by IR and ¹H and ¹³CNMR spectroscopy in solution, and by X-ray diffraction in the solid state. Compound 6 undergoes facile substitution of one of the 2-pyridyl groups by chloride, bromide, and methanosulfonate anions. Stable supramolecular adducts were formed between 7 and chloride, bromide, iodide, nitrate, and perrhenate anions. The solid state structures of these adducts (12-16) were determined by X-ray diffraction. Binding constants in dichloromethane were calculated from ¹HNMR titration data for all the new supramolecular adducts. The signal of the bridgehead C-H group is the one that undergoes a more pronounced downfield shift when tetrabutylammonium chloride was added to 7, whereas smaller shifts were found for the 2-pyridyl C(3)-H groups. In agreement, both types of C-H groups form hydrogen bonds to the anions in the solid state structures. Improved stability: New molybdenum and rhenium complexes are stable against ligand dissociation, and form stable supramolecular adducts with anions, employing C-H groups as the sole hydrogen bond donor groups (see figure).

Full text of DOI:10.1002/chem.201303653

DOI: 10.1002/chem.201303653
Full Paper
&
Metal Complexes
Interaction between Anions and Cationic Metal Complexes
Containing Tridentate Ligands with exo-CÀH Groups: Complex
Stability and Hydrogen Bonding
Hꢀctor Martꢁnez-Garcꢁa,[a] Dolores Morales,[a, b] Julio Pꢀrez,*[a] Marcos Puerto,[a] and
Ignacio del Rꢁo[a]
Abstract: [Re(CO)3([9]aneS3)][BAr’4] (1), prepared by reaction
of ReBr(CO)5, 1,4,7-trithiacyclononane ([9]aneS3) and NaBAr’4,
forms stable, soluble supramolecular adducts with chloride
(2), bromide, methanosulfonate (3) and fluoride (4) anions.
These new species were characterized by IR, NMR spectros-
copy and, for 2 and 3, also by X-ray diffraction. The results
of the solid state structure determinations indicate the for-
mation of CH···X hydrogen bonds between the anion (X) and
the exo-CÀH groups of the [9]aneS3 ligand, in accord with
methallyl)(CO)2(TpyCH)][BAr’4] (7) were synthesized by the re-
actions of [MoCl(h3-methallyl)(CO)2(NCMe)2], NaBAr’4 and
tris(2-pyridyl)amine (TpyN) or tris(2-pyridyl)methane (TpyCH)
respectively, and characterized by IR and 1H and 13C NMR
spectroscopy in solution, and by X-ray diffraction in the solid
state. Compound 6 undergoes facile substitution of one of
the 2-pyridyl groups by chloride, bromide, and methanosul-
fonate anions. Stable supramolecular adducts were formed
between 7 and chloride, bromide, iodide, nitrate, and
perrhenate anions. The solid state structures of these ad-
ducts (12–16) were determined by X-ray diffraction. Binding
1
the relatively large shifts found by H NMR spectroscopy in
dichloromethane solution for those hydrogens. The stability
of the chloride adduct contrasts with the lability of the
[9]aneS3 ligand in allyldicarbonyl molybdenum complexes re-
cently studied by us. With fluoride, in dichloromethane solu-
tion, a second, minor neutral dimeric species 5 is formed in
addition to 4. In 4, the deprotonation of a CÀH group of the
[9]aneS3 ligand, accompanied by CÀS bond cleavage and di-
merization, afforded 5, featuring bridging thiolates. Com-
pounds [Mo(h3-methallyl)(CO)2(TpyN)][BAr’4] (6) and [Mo(h3-
1
constants in dichloromethane were calculated from H NMR
titration data for all the new supramolecular adducts. The
signal of the bridgehead CÀH group is the one that under-
goes a more pronounced downfield shift when tetrabutyl-
ammonium chloride was added to 7, whereas smaller shifts
were found for the 2-pyridyl C(3)ÀH groups. In agreement,
both types of CÀH groups form hydrogen bonds to the
anions in the solid state structures.
cooperatively toward the anionic guest.[2] In most of these
hosts, the hydrogen bond donor groups are NÀH groups of
functions such as ammonium groups, amides, pyrroles, etc. In
some cases, appropriately placed CÀH groups can cooperate
with the NÀH groups.[3] Few hosts employ CÀH groups as the
only hydrogen bond donor groups and, among them, the Pd-
based receptor reported by Bedford, Tucker, and coworkers
has been the first that uses only aliphatic CÀH groups as hy-
drogen-bond donors.[4] In this receptor, coordination to the PdII
center rigidifies the ligand 1,4,7-trithiacyclononane ([9]aneS3) in
such a conformation that its exo-CÀH groups converge to-
wards an external anion. A weakness of this host, as with
many other metal-based hosts, is its lack of stability towards
the most nucleophilic anions. Thus, the Pd-based host undergo
displacement of the [9]aneS3 ligand in presence of chloride or
bromide. The cyclic thioether [9]aneS3 is, in general, a very
good ligand when it forms metal complexes acting as a fac-
capping tridentate ligand, because, in the most stable confor-
mation of the free ligand, the three sulfur atoms are disposed
in optimal orientations for metal complexation. As such, little
reorganization of the ligand is required for complex forma-
Introduction
Most synthetic anion receptors employ several hydrogen bond
donor groups placed in appropriate positions for anion bind-
ing, often in combination with the electrostatic attraction re-
sulting from a positive charge in the host.[1] This is also true of
one type of metal-based host, in which the metal, rather than
directly binding the anions, pre-organizes the set of ligands
and restricts their degrees of freedom, orienting their hydro-
gen bond donor groups in a convergent geometry, able to act
[a] Dr. H. Martꢀnez-Garcꢀa, Dr. D. Morales, Dr. J. Pꢁrez, Dr. M. Puerto,
Dr. I. del Rꢀo
Departamento de Quꢀmica Orgꢂnica e Inorgꢂnica- CINN
Facultad de Quꢀmica, Universidad de Oviedo-CSIC
33006 Oviedo (Spain)
Fax: (+34)985103446
E-mail: japm@uniovi.es
[b] Dr. D. Morales
Instituto Tecnolꢃgico de Materiales (ITMA). Parque Tecnolꢃgico de Asturias,
33428 Llanera (Asturias)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201303653.
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tion.[5] Inspired by the work of Bedford, Tucker, and coworkers,
we hypothesized that a metal fragment with a preference for
a pseudooctahedral geometry would form more stable com-
plexes with [9]aneS3 than the PdII center used by those au-
thors. Therefore, we synthesized and characterized complexes
of [9]aneS3 with the pseudooctahedral fragments Mo(methal-
lyl)(CO)2 and Mo(allyl)(CO)2, and studied their behavior in di-
chloromethane solution in the presence of several anions.[6]
The results demonstrated that the molybdenum complexes
were more stable than the Pd-based hosts, because the former
were stable in the presence of bromide; in fact, the solid-state
structure of the hydrogen bonded bromide-host ion pair could
be determined by X-ray diffraction. However, the more nucleo-
philic chloride anion completely and rapidly displaced the
[9]aneS3 ligand in dichloromethane solution at room tempera-
ture to form the known chloride-bridged binuclear anionic
Results
Rhenium trithiacyclononane compounds
The reaction of equimolar amounts of ReBr(CO)5, [9]aneS3, and
NaBAr’4 in refluxing toluene afforded the new compound
[Re(CO)3([9]aneS3)][BAr’4] (1) as the single product in 85% yield
as a white microcrystalline powder (Scheme 1). As is typical of
À
[Mo(h3-methallyl)(CO)2]2(m-Cl)3 complexes. In view of these re-
sults, we endeavored to synthesize more stable, cationic metal
complexes of [9]aneS3 and study their behavior toward anions,
including chloride. We have followed two different approaches
aiming to obtain hosts more stable than our previously report-
ed molybdenum complexes of [9]aneS3: first, we prepared
a complex of [9]aneS3 with the Re(CO)3 fragment. In compari-
sons between the two series of complexes, we have previously
found that rhenium tricarbonyl complexes are more stable
toward substitution of neutral ligands by anions than Mo-
(allyl)(CO)2 complexes.[7] Moreover, the compound [Re
(CO)3([9]aneS3)]Br was previously known, and its identity has
been conclusively demonstrated by X-ray diffraction.[8] Second,
since we have previously found that 2,2’-bipyridine, a bis(2-pyr-
idyl) ligand, forms with the Mo(methallyl)(CO)2 fragment, com-
plexes which are very stable in the presence of anions, includ-
ing chloride,[3b] we have employed that same metal fragment
in combination with the fac-capping tris(2-pyridyl)amine
(TpyN) and tris(2-pyridyl)methane (TpyCH) ligands,[9] under the
hypothesis that the CÀH groups at the backside of the coordi-
nated ligands would provide good hydrogen bond donor
groups toward external anions. The interaction between the
CÀH groups of metal-coordinated pyridines and anions has
been studied by Gale et al.[2h] Very recently, Sanford et al. re-
ported hydrogen bonding between chloride and other coun-
teranions and the pyridyl CÀH groups of a PdIV-coordinated
TpyCH ligand of the same type that will be discussed below.[10]
Constable et al. have demonstrated, both in solution and the
solid state, a significant interaction between chloride and the
3,3’-CH groups of a coordinated 2,2’-bipyridine ligand in an IrIII
complex.[11] A similar interaction has been found for RuII com-
plexes by Meyer et al.[12] In both approaches we have prepared
the cationic complexes as salts of the BAr’4 (Ar’=3,5-bis(tri-
fluoromethyl)phenyl),[13] because this anion has a very low ten-
dency to act as hydrogen bond acceptor[14] and, therefore,
should compete less than other counteranions with external
anions for hydrogen bonding the cationic host. Our results are
described in what follows.
Scheme 1. Synthesis of 1.
BAr’4 salts, 1 was found to be very soluble in dichloromethane
and non-aqueous oxygenated solvents such as tetrahydro-
furan, acetone, and diethylether. Its IR nCO bands (2058 and
1974 cmÀ1 in CH2Cl2) are consistent with the presence of a cat-
ionic fac-tricarbonyl complex.[15] The 1H NMR spectrum of 1 fea-
tures two multiplets for the CH2 groups of the [9]aneS3 ligand
(at 3.05 and 2.74 ppm in CD2Cl2, one for the endo and other
for the exo hydrogens), indicating that the trithioether ligand
does not dissociate (the 1H NMR of free [9]aneS3 consists of
one singlet), and the C3 symmetry of the complex. The three-
fold symmetry of the complex (which, in turn, indicates triden-
tate coordination of the [9]aneS3 ligand) was confirmed by the
presence of single signals for the CO (186.4 ppm) and [9]aneS3
(34.5 ppm) ligands in the 13C NMR spectrum of 1.
The behavior of 1 towards the tetrabutylammonium salts of
fluoride, chloride, bromide, iodide, hydrogensulfate, and meth-
anosulfonate in dichloromethane were studied by IR and
1H NMR spectroscopies. The unique behavior of fluoride will be
discussed below. The addition of tetrabutylammonium chloride
shifted the IR nCO bands of 1 only marginally to lower fre-
quencies, indicating hydrogen bonding, rather than formation
of a direct ReÀCl bond by a substitution reaction, in contrast
with the results found for the molybdenum complexes.[6] The
1
successive additions of [Bu4N]Cl shifted the H NMR multiplet
initially at 2.74 ppm to higher frequencies, whereas the signal
at 3.05 ppm remained virtually unchanged. This demonstrates
that the signal at 2.74 ppm in 1 corresponds to the exo hydro-
gens, pointing outward from the metal and, therefore, more
accessible for the contact with the anions (See Scheme 1). The
1
response of the H NMR chemical shift to the addition of hy-
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drogen-bond acceptors has been used to differentiate be-
tween hydrogens with different accessibility in polyamine com-
plexes.[16] Along the series of these additions of [Bu4N]Cl, only
[Bu4N]I, analogous precipitations took place, indicating that
the nature of the countercation does not affect the insolubility
of the species formed (PPN=bis(triphenylphosphoranylide-
ne)ammonium). Therefore, no further studied were carried out
with iodide and hydrogensulfate.
1
one set of signals were observed in the H NMR spectra, indi-
cating fast anion exchange. After addition of one equivalent of
[Bu4N]Cl, the magnitude of the shift spanned more than one
ppm. The variation of the chemical shift in response to the ad-
dition of chloride was used to generate a Job plot, shown in
the Supporting Information, which indicated the formation of
an adduct of 1:1 stoichiometry. A plot of the variation of the
chemical shift against the amount of chloride added is shown
in Figure 1. Treatment of these data with the WinEQNMR pro-
The synthesis and the solid state structural determination by
single crystal X-ray diffraction of compound [Re(-
CO)3([9]aneS3)]Br has been reported by Wieghardt and cowork-
ers.[8] The results demonstrate that the cation present in 1 is
stable towards displacement of the [9]aneS3 ligand by bro-
mide.
Equimolar amounts of 1 and tetrabutylammonium chloride
were combined in dichloromethane. After solvent evaporation
and washing the solid residue with diethylether to remove
[Bu4N][BAr’4], the compound [Re(CO)3([9]aneS3)]Cl (2) was crys-
tallized from dichloromethane/hexane. Its structure was deter-
mined by X-ray diffraction, and a thermal ellipsoid plot is
shown in Figure 2. Compound 2 consists of a C3v-symmetric
[Re(CO)3([9]aneS3)]+ complex with the chloride anion sitting on
top of the coordinated thioether and forming hydrogen bonds
with three of the exo CÀH groups. The relatively short C···Cl
distances, 3.551(0) angstrçms, and large C···H···Cl angles of
167.9(0) degrees, are consistent with significant CÀH···Cl hydro-
gen bonds, in agreement with the relatively large (for an ali-
gram[17] provided
a
104 value for the binding constant
(Table 1). This high value is in line with the saturation behavior
indicated by the horizontal line reached after one equivalent
of chloride was added.
1
phatic CÀH group) downfield shift of the H NMR signals of the
CÀH groups upon chloride addition described above.
Attempts to crystallize the methanosulfonate adduct by
a procedure analogous to that given above for 2 afforded the
hydrate [Re(CO)3([9]aneS3)][SO3Me]·H2O (3). Its structure, deter-
mined by X-ray diffraction, is shown in Figure 3. The three
oxygen atoms of the anion act as hydrogen-bond acceptors,
two of them with CÀH groups of the thioether ligand, and the
third with the water molecule. Despite the multi-point hydro-
gen bonding of the methanosulfonate anion, its binding con-
stant (Table 1) is lower than those with chloride and bromide,
as expected for an oxoanion, larger and with more charge de-
localization over the highly electronegative oxygen atoms.
Moreover, the fact that one of the oxygen atoms forms exclu-
sively a hydrogen bond with the water molecule suggests that
Figure 1. 1H NMR titration profile of 1 with [Bu4N]Cl in CD2Cl2.
A similar behavior has been found for bromide and metha-
nosulfonate (see Table 1 and the Supporting Information), with
slightly lower binding constants, as expected for larger anions.
When tetrabutylammonium salts of iodide and hydrogensul-
fate were added to 1, a large amount of a white precipitate,
quite insoluble in most organic solvents, was formed. When
tetraethylammonium iodide and [PPN]I were used in place of
Table 1. Stability constants of the cation complexes with various anions in the form of tetrabutylammonium salts; determined by 1H NMR titration in
CD2Cl2. Dd (ppm) max of the signal considered for Ka determination.
À
À
À
À
Receptor
1
ClÀ
BrÀ
IÀ
–
CH3SO3
HSO4
–
NO3
–
ReO4
–
Ka (MÀ1
Dd (ppm) 1.20
)
12729Æ826 11440Æ1572
7985Æ1125
0.82
1.11
Ka (MÀ1
)
515Æ93[a]
498Æ25[a]
54Æ5[a]
340Æ29[a]
89Æ11[a] 204Æ15[a]
98Æ13[b] 185Æ5[b]
447Æ100[b]
533Æ84[b]
113 Æ8[b]
324Æ19[b]
–
–
7
Dd (ppm) 2.65[c]
2.49[c]
1.06[d]
2.04[c]
1.02[d]
1.55[c]
0.80[d]
1.38[c]
0.63[d]
0.66[d]
0.37[d]
1.09[d]
Ka (MÀ1
Dd (ppm)
Ka (MÀ1
Dd (ppm)
)
–
–
2320Æ139
4699Æ257
2933Æ202
3839Æ685
–
–
–
–
[Mo(h3-methallyl)([9]aneS3)(CO)2]+[e]
[Mo(h3-allyl)([9]aneS3)(CO)2]+ [e]
0.97
0.86
0.75
0.69
–
)
11252Æ1503 14408Æ2301 15990Æ2514
0.98 0.87 0.75
[a] Stability constants determined by following bridgehead CH resonance and [b] H3 (py) resonance [c] Dd max determined from the titration curves fol-
lowing bridgehead CH and [d] H3 (py) resonance shift. [e] Related receptor complexes described in reference 6.
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nCO bands decreased slightly, in accordance with the forma-
tion of a hydrogen bonded ion pair [Re(CO)3([9]aneS3)]F (4),
1
like in the case of chloride or bromide. The H NMR spectrum
of 4 in CD2Cl2 displays multiplets at 3.75 and 2.94 ppm, diag-
nostic of coordinated, non-labile [9]aneS3. Compound 4 can be
trapped by carrying out the reaction between
1 and
tetrabutylammonium fluoride in diethylether, a good solvent
for both reagents, but in which 4 is insoluble and precipitates
as a white powder. However, in dichloromethane solution,
a second, minor species 5 is formed in addition to 4. Com-
pound 5 displays IR nCO bands at 2013 and 1917 cmÀ1. Initially,
these bands, much lower than those of 1, made us suspect of
a substitution of the thioether ligand by fluoride or by the hy-
droxide anion generated by water (the tetrabutylammonium
fluoride is a trihydrate) deprotonated by fluoride (Scheme 2),
because that was the case in the reaction of [Mo(h3-
methallyl)(CO)2([9]aneS3)][BAr’4] with tetrabuylammonium fluo-
1
ride.[6] However, H NMR spectra of the reaction crude did not
show the presence of free [9]aneS3. The product of the reac-
tion of 1 with [Bu4N]F·3H2O was washed with Et2O to remove
the [Bu4N][BAr’4] byproduct. The residue was dissolved in
CH2Cl2 and the resulting solution was layered with hexane and
allowed to slowly diffuse. Despite repeated attempts, we have
not been able to obtain X-ray quality crystals of 4. A single
crystal of 5 was employed for the determination of its solid-
state structure. Despite the low quality of the results, they
demonstrated that 5 is the neutral dimeric complex shown in
Figure 4.
Figure 2. Thermal-ellipsoid (50%) plot of 2. Main hydrogen bond distances
(ꢃ) and angles (8): C···Cl 3.551(0), C···H···Cl 167.9(0).
Figure 4. Thermal-ellipsoid (30%) plot of 5.
Molybdenum complexes of tris(2-pyridyl) ligands
Compounds [Mo(h3-methallyl)(CO)2(TpyN)][BAr’4] (6) and
[Mo(h3-methallyl)(CO)2(TpyCH)][BAr’4] (7) were synthesized by
Figure 3. Thermal-ellipsoid (30%) plot of 3. Main hydrogen bond distances
(ꢃ) and angles (8): C9ÀO4 3.564(0), C8ÀO5 3.405(0), C4ÀO5 3.307(0), O7ÀO4
2.843(0) O7ÀO6 2.906(0); C9-H9b-O4 169.53(0); C8-H8b-O5 151.84(0), C4-
H4a-O5 124.10(0), O7-H72-O4 163.75(0), O7-H71-O6 170.87(0).
[13]
the reactions of [MoCl(h3-methallyl)(CO)2(NCMe)2][18] NaBAr’4
and the ligands tris(2-pyridyl)amine (TpyN) or tris(2-pyridyl)me-
thane (TpyCH), respectively[9] (see Scheme 3), and characterized
1
by IR and H and 13C NMR spectroscopies in solution and by X-
ray diffraction in the solid state.
the presence of water, a better hydrogen bond donor than the
CÀH groups of the coordinated [9]aneS3, can exert a significant
screening of the interaction between the anion and the CÀH
groups.
The IR spectra of 6 and 7, each containing two broad nCO
bands, indicate their cis-dicarbonyl geometry, and the fact that
the more intense band is that at higher frequency indicates
acute OCÀMoÀCO angles.[6] The relatively high wavenumber
values of the IR nCO bands is in agreement with the presence
When compound 1 was treated with an equimolar amount
of tetrabutylammonium fluoride in dichloromethane, the IR
1
of cationic complexes. The H NMR spectra confirm the pres-
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discussed above, and, according-
ly, the methallyl groups display
an exo orientation. This contrasts
with the geometry found in our
compound
[Mo(h3-
methallyl)(CO)2([9]aneS3)][BAr’4],
in which the OCÀMoÀCO is
obtuse, and the methallyl ligand
is rotated.[6] The difference can
be attributed to the less steric
demand of the tris(2-pyridyl) li-
gands compared with 1,4,7-tri-
thiacyclononane.
The study of the behavior of
compounds 6 and 7 towards
several anions revealed a funda-
mental difference: the tris(2-pyri-
dyl)methane compound 7 was
stable; in contrast, the anions
studied were found to coordi-
Scheme 2. Proposed mechanism for the formation of 5.
Scheme 3. Synthesis of compounds 6 and 7.
Figure 5. Thermal-ellipsoid (50%) plot of the cation of 6.
ence of one BAr’4 anion per molybdenum; that is,
a BAr’4:methallyl:tris(2-pyridyl) ligand ratio of 1:1:1. The pres-
ence of separate signals for the syn and anti metallyl hydro-
gens indicates that the methallyl group is coordinated in
a static h3 mode. Two signals in a 1:2 ratio are observed for
the H6 hydrogens of the 2-pyridyl groups in the room temper-
nate the molybdenum atom of 6, displacing one of the 2-pyr-
idyl groups of the tris(2-pyridyl)amine ligand. These displace-
ment reactions were instantaneous and monitoring with IR
(featuring nCO bands significantly lower than those of the cat-
1
1
ature H NMR spectra of compounds 6 and 7, reflecting the ex-
ionic precursor) and H NMR spectroscopy failed to detect any
istence of a mirror plane in the cationic complexes, and their
rigidity. The latter contrasts with the dynamic behavior of
[9]aneS3 derivatives, which leads to apparent C3-symmetry at
room temperature.[6] The solid state structures of the cationic
complexes, shown in Figures 5 (6) and 6 (7), feature the tris(2-
pyridyl) ligands coordinated through their three nitrogen
atoms to cis-Mo(h3-methallyl)(CO)2 fragments. In these, the two
carbonyl groups and the metal form acute angles (80.7(3)8 in 6
and 84.14(18)8 in 7) in agreement with the solution IR spectra
intermediates. The resulting neutral complexes could be isolat-
ed for chloride (8), bromide (9) and methanosulfonate (10). In
their solid-state structures, determined by X-ray diffraction and
shown in Figure 4–6S (see the Supporting Information), one of
the coordinated 2-pyridyl groups is trans to one carbonyl
ligand, and the other, trans to the methallyl group, the anionic
ligand incorporated in the reaction is trans to the second car-
bonyl. Therefore, the structure is asymmetric. The room tem-
1
perature H NMR spectra of these neutral complexes reflect ap-
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Figure 6. Thermal-ellipsoid (50%) plot of the cation of 7.
parent molecular mirror planes. However, at low temperatures,
the spectra reflect asymmetric structures like those found in
the solid state (see Figure 7S in Supporting Information).
Therefore, the room temperature spectra are attributed to the
operation of a dynamic process, presumably a trigonal twist,
which is slowed down at low temperatures.
Figure 7. Thermal-ellipsoid (30%) plot of 11. Main hydrogen bond distances
(ꢃ) and angles (8): C32ÀO2 3.535(0), C43ÀO3 3.173(0), C42ÀO3 3.171(0); C32-
H32-O2 152.72(0), C43-H43-O3 133.55(0), C42-H42-O3 147.67(0).
When the product of the reaction between 6 and tetrabutyl-
ammonium methanosulfonate was crystallized by slow diffu-
sion of hexane into a dichloromethane solution, two different
types of crystals were obtained, one of them corresponding to
the neutral complex 10 mentioned above. The second type of
crystals was found to correspond to the hydrogen-bonded ion
pair 11. The structure of 11, an isomer of 10, is displayed in
Figure 7 and consists of an intact cationic complex like that in
compound 6, with a non-coordinated methanosulfonate anion.
The latter is hydrogen bonded through its oxygen atoms to
the hydrogen atoms of the CÀH groups in the 3-position of 2-
pyridyl groups. Structurally, compound 11 resembles the hy-
drogen-bonded ion pairs formed between the cationic tris(2-
pyridyl)methane complex from compound 7 and different
anions, which will be discussed below. However, unlike those
adducts that are stable in solution, and are the single products
of the reactions between 7 and the tetrabutylammonium salts
of several anions, compound 11 could only be isolated, accom-
panied by 10, by slow crystallization, and only the neutral
complex 10 could be spectroscopically detected when equi-
molar amounts of tetrabutylammonium methanosulfonate and
compound 6 were mixed in dichloromethane. These results in-
dicate that the formation of 10 is largely favored over that of
11, and that the crystallization of 11 from the solutions in
which 10 is the predominant (the only spectroscopically de-
tected) product results from the low solubility of 11. The fact
that no analogs of 11 with other anions could be obtained,
not even detected, is attributed to the higher nucleophilicity
of chloride and bromide compared to methanosulfonate.
The ion pairs formed by the cationic complex of 7 and chlo-
ride (12), bromide (13), iodide (14), nitrate (15) and perrhenate
(16) could be isolated (see the Experimental Section) as pure
crystalline solids, and their structures have been determined
by X-ray diffraction. The results are displayed in Figures 8–12.
Figure 8. Thermal-ellipsoid (50%) plot of 12. Main hydrogen bond distances
(ꢃ) and angles (8): C5ÀCl1 3.593(0), C52ÀCl1 3.488(0); C5-H5-Cl1 163.25(0),
C52-H52-Cl1 151.11(0).
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Figure 9. Thermal-ellipsoid (30%) plot of 13. Main hydrogen bond distances
(ꢃ) and angles (8): C5ÀBr1 3.708(0), C52ÀBr1 3.722(0), C5-H5-Br1 159.97(1),
C52-H52-Br1 150.99(1).
Figure 11. Thermal-ellipsoid (30%) plot of 15. Main hydrogen bond distan-
ces (ꢃ) and angles (8): C32ÀO1 3.478(0), C32ÀO3 3.405(0), C5ÀO1 3.305(0),
C52ÀO3 3.585(0); C32-H32-O1 145.55(0), C32-H32-O3 143.03(0), C5-H5-O1
175.57(0), C52-H52-O3 148.44(0).
2-pyridyl C(3)ÀH groups (See Figure 13). The signals corre-
sponding to the C(6)ÀH did not experience an appreciable
shift when four equivalents of Bu4NCl were added. From these
results it can be concluded that chloride approaches the cat-
ionic complex from the periphery of the tris(2-pyridyl)methane
ligand, in line with the solid-state structures discussed above.
Similar results were found with other anions (see the Support-
ing Information)
The Job plot for the interaction of 7 with chloride, using the
chemical shift of the bridgehead CH group (Figure 14) indi-
cates a 1:1 stoichiometry.
Figure 10. Thermal-ellipsoid (30%) plot of 14. Main hydrogen bond distan-
ces (ꢃ) and angles (8): C5ÀI1 3.890(0) C5-H5-I1 164.45(0).
Discussion
Our results demonstrate that the cationic rhenium complex
present in 1 is stable in the presence of the chloride anion in
dichloromethane solution, i.e., that the [9]aneS3 ligand is not
displaced by chloride, a nucleophilic anion in organic solvents
of low solvating power. This stands in contrast with the easy
displacement of the [9]aneS3 ligand by chloride in our recently
reported molybdenum allyl cationic complexes,[6] as well as
with the Pd complex reported by the groups of Bedford and
Tucker.[4] Results by Elias, Wieghardt, and coworkers indicate
that the manganese complex fac-[Mn(CO)3([9]aneS3)]+, analo-
gous to 1, is also stable in the presence of bromide and chlo-
In each case the anions approach the cationic complex so that
the closer contacts are those with the CÀH groups of the
tris(2-pyridyl)methane ligand. Some of these contacts, consis-
tent with weak hydrogen bonds, are marked with dashed lines
in the ORTEP diagrams. In solution, the interactions between 7
1
and the anions were investigated by H NMR spectroscopy. It
was found that the signal of the bridgehead CÀH group is the
one that undergoes a more pronounced downfield shift when
tetrabutylammonium chloride was added to a deuterated di-
chloromethane solution of 7. Smaller shifts were found for the
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Figure 14. Job plot for the titration of 7 with Bu4NCl.
Therefore, the presence of a third row metal (rhenium, in the
case of compound 1) is not a requisite for the stability of a cat-
ionic [9]aneS3 complex in the presence of chloride or bromide.
In the same line, cationic [9]aneS3 RhIII complexes are stable in
the presence of chloride.[20] The manganese and rhenium (I)
complexes, as well as these rhodium (III) complexes, have a d6
configuration, which contributes to the kinetic stability of the
complexes, a feature that is not present in the d4 molybdenum
(II) complexes, or in the d8 palladium (II) complexes, so perhaps
the stability associated to a d6 electronic configuration can be
one factor contributing to their different substitution behavior
towards chloride.
Figure 12. Thermal-ellipsoid (30) plot of 16. Main hydrogen bond distances
(ꢃ) and angles (8): C32ÀO4 3.475(0), C42ÀO4 3.435(0), C5ÀO4 3.274(0), C52À
O1 3.358(0); C32-H32-O4 140.17(0), C42-H42-O4 144.30(0), C5-H5-O4
160.25(0), C52-H52-O1 157.68(0).
The reaction of 1 with tetrabutylammonium fluoride results
in the formation of the dimeric complex 5, in which thiolate li-
gands, generated by ring opening of the trithiacyclononane li-
gands, bridge the two rhenium atoms. The formation of 5 can
be rationalized by the mechanism shown in Scheme 1, in
which the key feature is the deprotonation by fluoride (or hy-
droxide, since the fluoride salt contains water) of one of the
CÀH groups of the cationic rhenium complex, and the con-
comitant CÀS bond cleavage. The transformation of a cationic
complex (in 1) to the neutral complex 5 accounts for the large
decrease in the wavenumber values of the IR nCO bands. Re-
lated deprotonations of positively charged d6 complexes of
[9]aneS3, also involving CÀS bond cleavage and formation of
vinyl groups, have been demonstrated by Schrçder, Wieghardt
and coworkers for the homoleptic tricationic MIII
[M([9]aneS3)2]3+ (M=Co, Rh, Ir) coordination compounds[21]
and by Bennett and coworkers for the dicationic (arene)ruthe-
nium (II) [Ru(h6-C6Me6)([9]aneS3)]2+ organometallic complex.[22]
In these previous examples, the products were mononuclear
complexes in which the three different sulfur atoms of the
cleaved ligand remain bonded to the metal center. In contrast,
in compound 5, the sulfur bearing the vinyl group is uncoordi-
nated, and the thiolate sulfur acts as a bridge.
Figure 13. 1H NMR spectral changes observed when 7 is treated with in-
creasing amounts of [Bu4N]Cl.
ride counteranions.[19] The authors reported the preparation of
[Mn(CO)3([9]aneS3)]X (X=Cl, Br) by reaction of [Mn(CO)5X] with
[9]aneS3 in dimethylformamide and recrystallization of the
product in acetonitrile. Following anion exchange with
Binding constants for the stable molybdenum tris(2-pyridyl)-
1
[Bu4N][PF6],
they
isolated
crystals
of
composition
methane compound 7 (Table 1), calculated from the H NMR ti-
[Mn(CO)3([9]aneS3)]3(PF6)Br·2H2O, confirmed by X-ray diffraction.
trations represented in Figure 15 and Supporting Information,
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does not shed light on the rea-
sons of this dramatic difference.
However, the structures of the
neutral products 8, 9, and 10
provide an explanation: The co-
ordination around the bridge-
head nitrogen atom is planar, as
indicated by the sum of the
angles about it, 3608. Therefore,
dissociation of one of the 2-pyr-
idyl groups allows for the attain-
ing of this planarity. Literature
searches showed that planarity
at the central nitrogen is always
Figure 15. 1H NMR titration profiles of 7 with Bu4NCl.
found in free tris(2-pyridyl)a-
mine[23] and related compounds
were found to be very small compared with those found for
the molybdenum[6] and rhenium (compound 1, see above)
complexes of the [9]aneS3 ligand. At least in part, the differ-
ence can be attributed to the presence of the sulfur atoms,
electronegative and directly bonded to the cationic metal
center, in the [9]aneS3 complexes, which would increase the
acidity of the adjacent CÀH groups. In addition, in the com-
plexes of the [9]aneS3 ligand, an anion can interact simultane-
ously with three of the CÀH exo-groups, whereas in the case of
the tris(2-pyridyl) hosts, the solid state structures for chloride
and bromide show than the significant interactions are with
the CÀH bridgehead group and with one of the aryl CÀH
groups (Figure 16).
as well as in other metal complexes with bidentate tris(2-pyri-
dyl)amine ligands,[24] reflecting a more stable conformation.
This higher stability can be traced to the delocalization of the
nitrogen lone pair involving the aryl rings. These results sug-
gests that, in general, complexes of the tris(2-pyridyl)amine
will be less stable against substitution than those of, for in-
stance, tris(2-pyridyl)methane, which lack lone pairs at the
bridgehead atom.
Conclusion
Two types of metal-complex-based anion hosts have been syn-
thesized, which are more stable against ligand substitution by
anions than our previously reported allyldicarbonyl molybde-
num-based hosts [Mo(h3-methallyl)(CO)2([9]aneS3)][BAr’4] and
[Mo(h3-allyl)(CO)2([9]aneS3)][BAr’4]: rhenium tricarbonyl trithiacy-
clononane complexes, and allyldicarbonyl molybdenum com-
plexes of tris(2-pyridyl)methane. Tris(2-pyridyl)amine analogs of
the later have been found to undergo facile substitution of
one of the 2-pyridyl groups by anions, presumably reflecting
the tendency of tris(2-pyridyl)amine to become planar at nitro-
gen. Ion pairs formed between several simple inorganic anions
and the stable cationic rhenium and molybdenum complexes
could be isolated, and their solid state structures, determined
by X-ray diffraction, show hydrogen bonding between CÀH
groups of the [9]aneS3 or TpyCH ligands and the anions. Fluo-
ride deprotonates the [9]aneS3 ligand of the rhenium complex
to afford a dimeric, thiolato-bridged complex. 1H NMR spec-
troscopy demonstrates that the interactions between the
anions and the CÀH groups at the periphery of the cationic
complexes persist in dichloromethane solution, and allowed to
establish the 1:1 stoichiometry of the adducts, and to calculate
the binding constants. Binding constants have been found to
be larger for the rhenium hosts.
Figure 16. Host-anion binding.
In spite of their relatively low stability, shown by the small
binding constants (Table 1), the ion pairs formed by the tris(2-
pyridyl) molybdenum complexes with several anions, have
been demonstrated to be stable to permit their isolation as
pure crystalline solids.
The tris(2-pyridyl) complexes have been found to be inert
against the displacement of the coordinated 2-pyridyl groups
by anions, even in the presence of an excess of the relatively
nucleophilic chloride anion in low-solvating dichloromethane,
or for long periods of time, like those needed for slow diffu-
sion crystallization (typically, several days). This behavior stands
in sharp contrast to the easy substitution of one of the 2-pyrid-
yl groups in the complex of tris(2-pyridyl)amine discussed
above. A comparison of the data of the compounds 6 and 7
Experimental Section
All manipulations were carried out at room temperature under a di-
nitrogen atmosphere employing Schlenk techniques. CH2Cl2 was
dried over CaH2, diethylether over Na-benzophenone, and hexane
and toluene over sodium. IR and NMR spectra were recorded on
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Perkin–Elmer FT1720-X and Bruker AV-400 or AV-300 spectrometers
respectively. Deuterated solvents were degassed by three freeze-
pump-thaw cycles, dried over 4 ꢃ molecular sieves and stored in
the dark. [ReBr(CO)5][25] and [MoCl(h3-methallyl)(CO)2(NCMe)2][18]
(methallyl=C3H4-Me-2) were prepared according to literature pro-
cedures. All other chemicals were purchased and used without fur-
ther purification. The characterization labeling Scheme is shown in
Figure 17.
(m, 6H; CH2 of [9]aneS3), 2.59 ppm (s, 3H; CH3SO3); IR (CH2Cl2) n˜ =
2050 (vs), 1962 cmÀ1 (s); elemental analysis calcd (%) for
C10H15O6ReS4·H2O (563.69): C 21.31, H 3.04; found: C 21.40, H 3.08.
Reaction of 1 with [nBu4N]F·3H2O: A solution of 1 (0.100 g,
0.076 mmol) and [nBu4N]F·3H2O (0.023 g, 0.076 mmol) in CH2Cl2
(10 mL) was stirred for 30 min. The IR of the reaction crude at this
point shows the presence of several species. The solvent was
evaporated and the white solid residue was extracted
with diethylether (3ꢄ10 mL). The white solid insoluble
in ether was found to be [Re(CO)3([9]aneS3)]·F (4). Yield:
0.999 g, 28%. 1H NMR (400 MHz, CD2Cl2): d=3.75 (m,
6H; CH2 of [9]aneS3), 2.94 ppm (m, 6H; CH2 of [9]aneS3);
Limited solubility precluded the acquisition of its
13C NMR spectrum; IR (CH2Cl2) n˜ =2050 (vs), 1961 cmÀ1
(s); elemental analysis calcd (%) for C9H12FO3ReS3
(469.58): C 23.02, H 2.58; found: C 23.11, H 2.63. The
Figure 17. Labeling Scheme for BAr’4, methallyl, exo hydrogens of [9]aneS3 and 2-pyridyl.
ether washings were collected, the solvent was evapo-
rated and the resulting solid was found to contain 5,
[nBu4N][BAr’4] and some non-identified compounds.
Crystallization from CH2Cl2/hexane afforded solids enriched in 5.
1H NMR (400 MHz, CD2Cl2): d=6.43 (m, 2H; CH), 5.25 (m, 4H; CH2
terminal), 3.15–2.90 ppm (m, 16H; CH2); IR (CH2Cl2) n˜ =2013 (vs),
1917 cmÀ1 (s). However, 5 was always contaminated with non-iden-
tified compounds and we have been unable to obtain spectro-
scopically pure samples. Repeated attempts to purify 5 by crystalli-
zation failed to provide samples of analytical purity, or amounts of
crystals enough for NMR samples. Our crystal resulting from one of
these crystallizations (slow diffusion of hexane into a concentrated
solution of 5 was used for the structural characterization by X-ray
diffraction.
[Re(CO)3([9]aneS3)][BAr’4] (1): A mixture of [ReBr(CO)5] (0.250 g,
0.610 mmol) and [9]aneS3 (0.111 g, 0.610 mmol) was heated to
reflux in toluene for 1 h. The solution was allowed to reach room
temperature obtaining a white precipitate. After removal of tolu-
ene the solid was dried in vacuo and dissolved in CH2Cl2 (30 mL)
and NaBAr’4 (0.540 g, 0.610 mmol) was added. The reaction mixture
was stirred at room temperature overnight. After filtration through
diatomaceous earth the filtrate was reduced to 5 mL. Addition of
hexane resulted in the formation of a microcrystalline white solid
which was washed with hexane (3ꢄ10 mL) and dried under re-
1
duced pressure. Yield: 0.682 g, 85%. H NMR (400 MHz, CD2Cl2): d=
[Mo(h3-methallyl)(CO)2(TpyN)][BAr’4] (6): A mixture of [MoCl(h3-
methallyl)(CO)2(MeCN)2] (0.110 g, 0.339 mmol), TpyN (0.084 g,
0.039 mmol) and NaBAr’4 (0.300 g, 0.339 mmol) in CH2Cl2 (15 mL)
was stirred for 1 h. After filtration through diatomaceous earth the
filtrate was reduced to 5 mL. Addition of hexane resulted in the
formation of orange crystals (2 days at À208C), one of which was
used for X-ray analysis (0.350 g, 78%). 1H NMR (300 MHz, CD2Cl2):
d=9.54 (sbr, 1H; Hpy), 9.05 (sbr, 2H; Hpy), 8.04 (m, 3H; Hpy), 7.85 (m,
11 H ; 8Ho of BAr’4 and 3Hpy), 7.56 (m, 7H; 4Hp of BAr’4 and 3Hpy),
3.65 (s, 2H; Hsyn), 1.87 (s, 2H; Hanti), 1.56 ppm (s, 3H; CH3 of methall-
yl); 13C{1H} NMR (75 MHz, CD2Cl2): d=227.5 (s; CO), 164.5 (c,
J(C,B)=49.8 Hz; Ci of BAr’4), 155.8 (s; py), 146.3 (s; py), 137.2 (s; Co
of BAr’4), 131.3 (m; Cm of BAr’4), 129.2 (s, 2C; py), 128.7 (s; py),
126.9 (c J(C,F)=272.5; CF3 of BAr’4), 119.9 (s; Cp of BAr’4), 88.4 (s; Cc
of methallyl), 64.9 (s; Ct of methallyl), 20.5 ppm (s; CH3 of methall-
yl); IR (CH2Cl2) n˜ =1957 (vs), 1872 cmÀ1 (s); elemental analysis calcd
(%) for C53H31BF24MoN4O2·CH2Cl2 (1403.50) C 46.15, H 2.37; N, 3.99;
found: C 45.93, H 2.46, N 4.11.
[Mo(h3-methallyl)(CO)2(TpyCH)][BAr’4] (7): A mixture of [MoCl(h3-
methallyl)(CO)2(MeCN)2] (0.080 g, 0.245 mmol), TpyCH (0.060 g,
0.245 mmol) and NaBAr’4 (0.215 g, 0.245 mmol) in CH2Cl2 (15 mL)
was stirred for 1 h. After filtration through diatomaceous earth, the
solvent was removed in vacuo. The orange residue was washed
with hexane (3ꢄ10 mL). By slow diffusion of hexane into a concen-
trated solution of 7 in CH2Cl2 at À208C orange crystals were ob-
tained (0.190 g, 60%), one of which was used for X-ray analysis.
1H NMR (300 MHz, CD2Cl2): d=9.71 (sbr, 1H; H6 pytrans), 8.91 (s, 2H;
H6 pycis), 7.93 (td, J=7.7, 1.6 Hz, 3H; Hpy), 7.83 (s, 8H; Ho of BAr’4),
7.76 (d, J=5.9 Hz, 3H; Hpy), 7.64 (s, 4H; Hp of BAr’4), 7.47 (sbr, 3H;
Hpy), 5.75 (s, 1H; CÀH), 3.61 (s, 2H; Hsyn), 1.98 (s, 2H; Hanti), 1.82 ppm
(s, 3H; CH3 of methallyl); 13C{1H} NMR (75 MHz, CD2Cl2): d=229.2
(s; CO), 163.4 (c J(C,B)=49.8 Hz; Ci of BAr’4), 159.5 (s; py), 156.7 (s;
py), 155.9 (s; py), 144.8 (s; py), 144.2 (s; py), 137.0 (s; Co of BAr’4),
7.79 (s, 8H; Ho of BAr’4), 7.64 (s, 4H; Hp of BAr’4), 3.05 (m, 6H; CH2
of [9]aneS3), 2.74 ppm (m, 6H; CH2 of [9]aneS3); 13C{1H}NMR
(100 MHz, CD2Cl2): d=186.4 (s, CO), 161.7 (c, J(C, B)=50.2 Hz, Ci of
BAr’4), 134.7 (s, Co of BAr’4), 128.7 (m, Cm of BAr’4), 124.6 (c, J(C, F)=
272.7 Hz, CF3 of BAr’4), 117.5 (s, Cp of BAr’4), 34.5 ppm (s, CH2 of
[9]aneS3); IR (CH2Cl2) n˜ =2058 (vs), 1974 cmÀ1(s); elemental analysis
calcd (%) for C41H24BF24O3ReS3 (1313.80): C 37.44, H 1.84; found: C
37.59, H 2.03.
[Re(CO)3([9]aneS3)]·Cl (2): A solution of 1 (0.100 g, 0.076 mmol)
and [nBu4N]Cl (0.021 g, 0.076 mmol) in CH2Cl2 (10 mL) was stirred
for 30 min. After evaporation of the solvent, the white residue was
washed with diethylether (3ꢄ5 mL) (to remove the [nBu4N][BAr’4]
salt) and dried in vacuo. By slow diffusion of hexane into a concen-
trated solution of 2 in CH2Cl2 at À208C, colorless crystals of good
quality (0.036 g, 88%) for the determination of the structure by X-
1
ray analysis were obtained. H NMR (400 MHz, CD2Cl2): d=4.00 (m,
6H, CH2 of [9]aneS3), 2.96 ppm (m, 6H, CH2 of [9]aneS3); 13C{1H}
NMR (100 MHz, CD2Cl2): d=188.2 (s; CO), 35.9 ppm (s; CH2 of
[9]aneS3); IR (CH2Cl2): n˜ =2050 (vs), 1961 cmÀ1 (s); elemental analy-
sis calcd (%) for C9H12ClO3ReS3·3H2O (540.08): C 22.23, H 2.49;
found: C 22.55, H 2.54.
[Re(CO)3([9]aneS3)]·Br: This compound was prepared in a similar
way to 2 starting from 1 (0.100 g, 0.076 mmol) and [nBu4N]Br
(0.024 g, 0.076 mmol) to yield 0.031 g (77%). 1H NMR (300 MHz,
CD2Cl2): d=3.85 (m, 6H; CH2 of [9]aneS3), 2.98 ppm (m, 6H; CH2 of
[9]aneS3); IR (CH2Cl2) n˜ =2051 (vs), 1962 cmÀ1 (s); elemental analysis
calcd (%) for C9H12BrO3ReS3 (530.48) C 20.38, H 2.28; found: C
20.05, H 2.42.
[Re(CO)3([9]aneS3)]·[CH3SO3] (3): This compound was prepared as
described above for 2 starting from 1 (0.100 g, 0.076 mmol) and
[nBu4N][CH3SO3] (0.026 g, 0.076 mmol) to yield colorless crystals
(0.034 g, 79%), one of which was used for an X ray analysis.
1H NMR (400 MHz, CD2Cl2): d=3.61 (m, 6H; CH2 of [9]aneS3), 2.96
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131.6 (m; Cm of BAr’4), 129.6 (s; py), 127.3 (s; py), 127.2 (s; py),
126.9 (c, J(C,F)=272.5; CF3 of BAr’4), 119.9 (s; Cp of BAr’4), 91.3 (s; Cc
of methallyl), 66.7 (s; Ct of methallyl), 63.1 (s; CÀH), 20.9 ppm (s;
CH3 of methallyl); IR (CH2Cl2) n˜ =1955 (vs), 1867 cmÀ1 (s); elemental
analysis calcd (%) for C54H32BF24MoN3O2 (1317.58): C 49.12, H 2.44,
N 3.18; found: C 49.24, H, 2.40; N, 3.06.
[Mo(h3-methallyl)(CO)2(TpyCH)]·Cl (12): A mixture of 7 (0.050 g,
0.038 mmol) and [nBu4N]Cl (0.014 g, 0.038 mmol) in CH2Cl2 (15 mL)
was stirred for 30 min. After evaporation of the solvent under
vacuum the resulting yellow residue was washed with diethylether
(3ꢄ10 mL) (to remove the [nBu4N][BAr’4] salt) and dried in vacuo.
By slow diffusion of hexane into a concentrated solution of 12 in
CH2Cl2 at À208C, yellow crystals of good quality (0.016 g, 86%) for
the determination of the structure by X-ray analysis were obtained.
1H NMR (300 MHz, CD2Cl2): d=9.59 (sbr, 1H; Hpy), 8.89 (sbr, 5H; Hpy),
8.54 (s, 1H; CÀH), 7.99 (t (8.0), 3H; Hpy), 7.43 (sbr, 3H; Hpy), 3.58 (s,
2H; Hsyn), 1.86 (s, 2H; Hanti), 1.71 ppm (s, 3H; CH3 of methallyl);
13C{1H} NMR (75 MHz, CD2Cl2): 226.7 (s; CO), 155.6 (s; py), 151.9 (s;
py), 141.9 (s; py), 128.7 (s; py), 123.9 (s; py), 88.6 (s; Cc of methallyl),
64.1 (s; Ct of methallyl), 56.8 (s; CÀH), 19.2 ppm (s; CH3 of methall-
yl); IR (CH2Cl2) n˜ =1950 (vs), 1860 cmÀ1 (s); elemental analysis calcd
(%) for C22H20ClMoN3O2 (489.81): C 53.95; H 4.11, N 8.58; found: C
54.10, H 4.23, N 8.78.
[MoCl(h3-methallyl)(CO)2(TpyN)] (8): Method A) A solution of 6
(0.100 g, 0.076 mmol) and [nBu4N]Cl (0.021 g, 0.076 mmol) was
stirred for 30 min. The solvent was removed under vacuum and
the resulting yellow residue was washed with diethylether (3ꢄ
10 mL) and dried in vacuo. By slow diffusion of hexane into a con-
centrated solution of 8 in CH2Cl2 at À208C yellow crystals of good
quality (0.030 g, 80%) for the determination of the structure by X-
1
ray analysis were obtained. H NMR (300 MHz, CD2Cl2): 8.85 (d, J=
4.7 Hz, 2H; Hpy coord), 8.35 (d, J=3.9 Hz, 1H; Hpy uncoord), 7.89 (m, 4H;
2Hpy
and 2Hpy uncoord), 7.72 (m, 1H; Hpy uncoord), 7.37 (s, 2H; Hpy
coord
coord), 7.06 (m, 2H; Hpy coord), 3.07 (s, 2H; Hsyn), 2.59 (s, 3H; CH3 of
methallyl), 1.26 ppm (s, 2H; Hanti); 13C{1H} NMR (75 MHz, CD2Cl2):
d=226.8 (s; CO), 154.3 (s; py), 152.5 (s; py), 152.0 (s; py), 147.6 (s;
py), 139.0 (s; py), 138.2 (s; py), 124.0 (s; py), 122.4 (s; py), 118.1 (s;
py), 110.4 (s; py), 83.7 (s; Cc of methallyl), 57.1 (s; Ct of methallyl),
20.9 ppm (s; CH3 of methallyl); IR (CH2Cl2) n˜ =1934 (vs),
1842 cmÀ1(s); elemental analysis calcd (%) for C21H19ClMoN4O2
(490.80) C 51.39, H 3.90, N 11.42; found: C 51.18, H 3.78, N 11.27.
Method B) A mixture of [MoCl(h3-methallyl)(CO)2(MeCN)2] (0.030 g,
0.092 mmol) and TpyN (0.023 g, 0.092 mmol) in CH2Cl2 (15 mL) was
stirred for 3 h. Spectroscopic and analytical data of the product ob-
tained agree with those obtained by method A.
[Mo(h3-methallyl)(CO)2(TpyCH)]·Br (13): This compound was pre-
pared as described above for 12 starting from
7 (0.100 g,
0.076 mmol) and [nBu4N]Br (0.024 g, 0.076 mmol) to yield orange
crystals (0.033 g, 81%), one of which was used for an X ray analy-
1
sis. H NMR (400 MHz, CD2Cl2): d=9.60 (sbr, 1H; Hpy), 8.86 (sbr, 2H;
Hpy), 8.77 (sbr, 2H; Hpy), 8.58 (sbr, 1H; Hpy), 8.37 (s, 1H; CÀH), 8.01 (t
(7.7), 3H; Hpy), 7.43 (sbr, 3H; Hpy), 3.58 (s, 2H; Hsyn), 1.87 (s, 2H; Hanti),
1.72 ppm (s, 3H; CH3 of methallyl); 13C{1H} NMR (100 MHz, CD2Cl2):
d=226.7 (s; CO), 155.4 (s; py), 151.9 (s; py), 141.1 (s; py), 128.5 (s;
py), 123.9 (s; py), 88.7 (s; Cc of methallyl), 64.1 (s; Ct of methallyl),
56.7 (s; CÀH), 19.2 ppm (s; CH3 of methallyl); IR (CH2Cl2) n˜ =1951
(vs), 1862 cmÀ1 (s); elemental analysis calcd (%) for C22H20BrMoN3O2
(534.26): C 49.46, H 3.77, N 7.86; found: C 49.50, H 3.86, N, 8.09.
[MoBr(h3-methallyl)(CO)2(TpyN)] (9): A mixture of 6 (0.100 g,
0.076 mmol) and [nBu4N]Br (0.024 g, 0.076 mmol) was stirred for
30 min. After evaporation of the solvent under vacuum, the residue
was washed with diethylether (3ꢄ5 mL), dried in vacuo and the re-
sulting solid was dissolved in CH2Cl2. This solution was layered
with hexane (20 mL) and orange crystals were obtained from slow
[Mo(h3-methallyl)(CO)2(TpyCH)]·I
(14):
[nBu4N]I
(0.014 g,
0.038 mmol) was added to a solution of 7 (0.050 g, 0.038 mmol) in
CH2Cl2 (15 mL) and the reaction mixture was stirred for 30 min. The
rest of the procedure is similar to that described for 11, including
the solid-state determination by means of X-ray analysis. Yield:
1
1
diffusion at À208C. (0.033 g, 82%). H NMR (400 MHz, CD2Cl2): d=
0.019 g, 86%. H NMR (300 MHz, CD2Cl2): d=9.63 (sbr, 1H; Hpy), 8.83
9.02 (d, J=5.0 Hz, 2H; Hpy coord), 8.34 (d, J=3.8 Hz, 1H; Hpy uncoord),
8.02 (m, 2H; Hpy coord), 7.87 (s, 1H; Hpy uncoord), 7.86 (s, 1H; Hpy uncoord),
7.71 (m, 1H; Hpy uncoord), 7.36 (m, 2H; Hpy coord), 7.05 (m, 2H; Hpy coord),
3.13 (s, 2H; Hsyn), 2.68 (s, 3H; CH3 of methallyl), 1.27 ppm (s, 2H;
Hanti); 13C{1H} NMR (100 MHz, CD2Cl2): d=226.6 (s; CO), 154.3 (s; py),
152.9 (s; py), 152.5 (s; py), 147.6 (s; py), 139.1 (s; py], 138.2 (s; py],
124.0 (s; py], 122.3 (s; py], 118.1 (s; py], 110.4 (s; py], 83.5 (s; Cc of
methallyl], 56.9 (s; Ct of methallyl], 21.7 ppm (s; CH3 of methallyl];
IR (CH2Cl2) n˜ =1937 vs, 1847 cmÀ1 (s); elemental analysis calcd (%)
for C21H19BrMoN4O2 (535.25): C 47.12, H 3.58, N 10.47; found: C
47.21, H 3.68, N 10.66.
(sbr, 5H; Hpy), 8.02 (t (7.6), 3H; Hpy), 7.99 (s, 1H; CÀH), 7.45 (sbr, 3H;
Hpy), 3.58 (s, 2H; Hsyn), 1.89 (s, 2H; Hanti), 1.74 ppm (s, 3H; CH3 of
methallyl); 13C{1H} NMR (75 MHz, CD2Cl2): d=226.6 (s; CO), 155.1 (s;
py), 152.5 (s; py), 141.2 (s; py), 128.2 (s; py), 124.1 (s; py), 89.0 (s; Cc
of methallyl), 64.3 (s; Ct of methallyl), 56.8 (s; CÀH), 19.3 ppm (s;
CH3 of methallyl); IR (CH2Cl2) n˜ =1952 (vs), 1862 cmÀ1 (s); elemental
analysis calcd (%) for C22H20IMoN3O2 (581.26): C 45.46, H 3.47, N
7.23; found: C 45.23, H 3.44, N 7.31.
[Mo(h3-methallyl)(CO)2(TpyCH)]·[CH3SO3]: The procedure is similar
to that described for the other adducts, but starting from 7
(0.100 g, 0.076 mmol) and [nBu4N][CH3SO3] (0.026 g, 0.076 mmol).
Yield: 0.035 g, 84%. 1H NMR (400 MHz, CD2Cl2): d=9.61 (sbr, 1H;
Hpy), 8.82 (sbr, 2H; Hpy), 8.69 (sbr, 1H; Hpy), 8.58 (sbr, 2H; Hpy), 8.02 (t
(7.4), 3H; Hpy), 7.43 (s, 4H; 3Hpy and CÀH), 3.65 (s, 2H; Hsyn), 2.84 (s,
3H; CH3SO3), 1.89 (s, 2H; Hanti), 1.66 ppm (s, 3H; CH3 of methallyl);
13C{1H} NMR (100 MHz, CD2Cl2): d=226.7 (s; CO), 155.2 (s; py),
151.9 (s; py), 141.4 (s; py), 128.7 (s; py), 123.9 (s; py), 88.8 (s; Cc of
methallyl), 64.0 (s; Ct of methallyl), 58.4 (s; CÀH), 39.7 (s; CH3SO3),
19.3 ppm (s; CH3 of methallyl); IR (CH2Cl2) n˜ =1951 (vs), 1862 cmÀ1
(s); elemental analysis calcd (%) for C23H23MoN3O5S (549.45): C
50.27, H 4.21, N 7.65; found: C 50.18, H 4.33, N, 7.59.
[Mo(CH3SO3)(h3-methallyl)(CO)2(TpyN)] (10): This compound was
prepared in
a similar way to 8 starting from 6 (0.100 g,
0.076 mmol) and [nBu4N][CH3SO3] (0.026 g, 0.076 mmol) to yield
orange crystals (0.036 g, 75%), one of which was used for X-ray
1
analysis. H NMR (400 MHz, CD2Cl2): d=8.92 (d, J=5.0 Hz, 2H; Hpy
coord], 8.34 (sbr, 1H; Hpy uncoord), 7.94 (m, 4H; 2Hpy
and 2Hpy uncoord),
coord
7.73 (m, 1H; Hpy uncoord), 7.43 (m, 2H; Hpy coord), 7.05 (m, 2H; Hpy coord),
3.48 (s, 2H; Hsyn), 2.63 (s, 3H; CH3 of methallyl), 2.50 (s, 3H;
CH3SO3), 1.29 ppm (s, 2H; Hanti); 13C{1H} NMR (100 MHz, CD2Cl2): d=
227.5 (s; CO), 154.1 (s; py), 152.1 (s; py), 151.3 (s; py), 147.6 (s; py),
139.3 (s; py), 138.3 (s; py), 124.4 (s; py), 122.6 (s; py), 118.3 (s; py),
110.4 (s; py), 83.7 (s; Cc of methallyl), 57.1 (s; Ct of methallyl), 40.5
(s; CH3SO3) 20.9 ppm (s; CH3 of methallyl); IR (CH2Cl2) n˜ =1942 (vs),
[Mo(h3-methallyl)(CO)2(TpyCH)]·[NO3] (15): It was synthesized in
a similar way than 12, starting from 7 (0.050 g, 0.038 mmol) and
[nBu4N][NO3] (0.012 g, 0.038 mmol). By slow diffusion of hexane
into a concentrated solution of 15 in CH2Cl2 yellow crystals were
obtained for an X-ray analysis. Yield: 0.016 g, 81%. 1H NMR
(300 MHz, CD2Cl2): d=9.61 (sbr, 1H; Hpy), 8.87 (sbr, 2H; Hpy), 8.46 (sbr,
1848
(s) cmÀ1
;
elemental
analysis
calcd
(%)
for
C22H22MoN4O5S·CH2Cl2 (635.37): C 43.47, H 3.81, N 8.82; found: C
43.21, H 3.61, N 8.56.
Chem. Eur. J. 2014, 20, 5821 – 5834
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3H; Hpy), 8.02 (t (7.8), 3H; Hpy), 7.45 (s, 3H; Hpy), 7.26 (s, CÀH), 3.59
(s, 2H; Hsyn), 1.89 (s, 2H; Hanti), 1.75 ppm (s, 3H; CH3 of methallyl);
13C{1H} NMR (75 MHz, CD2Cl2): d=226.7 (s; CO), 154.9 (s; py), 152.1
(s; py), 141.4 (s; py), 128.2 (s; py), 124.1 (s; py), 89.2 (s; Cc of meth-
allyl), 64.3 (s; Ct of methallyl), 59.3 (s; CÀH), 19.4 ppm (s; CH3 of
methallyl); IR (CH2Cl2) n˜ =1952 (vs), 1862 cmÀ1 (s); elemental analy-
sis calcd (%) for C22H20MoN4O5 (516.36): C 51.17, H 3.90, N 10.85;
found: C 51.32, H 3.80, N 10.49.
C22H20MoN3O6Re·CH2Cl2 (789.50): C 36.64, H 2.94, N 5.57; found: C
36.76, H 2.82, N, 5.33.
X-Ray Diffraction Analysis: Selected crystal and refinement data
are given in Table 2. Diffraction data for 6 and 7 were collected on
a Nonius Kappa-CCD diffractometer, using graphite-monochromat-
ed Mo-Ka radiation. A semi-empirical absorption correction was
performed with SORTAV.[26] Diffraction data for 2, 3 and 8--16 were
collected on a Oxford Diffraction Xcalibur Nova single crystal dif-
fractometer, using Cu-Ka radiation. Empirical absorption correc-
tions were applied using the SCALE3 ABSPACK algorithm as imple-
mented in the program CrysAlis Pro RED (Oxford Diffraction Ltd.,
2006).[27] Structures were solved by Patterson interpretation using
the program SIR2004.[28] Isotropic and full matrix anisotropic least
square refinements were carried out using SHELXL.[29] H(5) hydro-
gen atom positions in 5 and 14 were located in the corresponding
Fourier difference maps and were refined without restrictions. All
the other hydrogen atoms were set in calculated positions and re-
fined riding on their parent atoms. The molecular plots were made
with the PLATON program package.[30] The WINGX program
system[31] was used throughout the structure determinations. A se-
[Mo(h3-methallyl)(CO)2(TpyCH)]·[ReO4] (16): As it was described
above, starting from 7 (0.050 g, 0.038 mmol) and [nBu4N][ReO4]
(0.012 g, 0.038 mmol), yellow crystals of good quality (0.022 g,
73%) for the determination of the structure of 16 by X-ray analysis
were obtained. 1H NMR (300 MHz, CD2Cl2): d=9.61 (sbr, 1H; Hpy),
8.88 (sbr, 2H; Hpy), 8.23 (sbr, 3H;Hpy), 8.05 (t (7.7), 3H; Hpy), 7.49 (sbr,
3H; Hpy), 6.56 (s, CÀH), 3.59 (s, 2H; Hsyn), 1.91 (s, 2H; Hanti), 1.78 ppm
(s, 3H; CH3 of methallyl); 13C{1H} NMR (75 MHz, CD2Cl2): d=226.6
(s; CO), 154.3 (s; py), 152.4 (s; py), 141.6 (s; py), 127.8 (s; py), 124.4
(s; py), 89.8 (s; Cc of methallyl), 64.5 (s; Ct of methallyl), 60.9 (s; CÀ
H), 19.5 ppm (s; CH3 of methallyl); IR (CH2Cl2) n˜ =1953 (vs),
1864 cmÀ1
(s);
elemental
analysis
calcd
(%)
for
Table 2. Crystal data and refinement details for complexes 2, 3, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16.
2
3
6
7
empirical formula
Mr
C9H12ClO3ReS3·3H2O
540.06
C10H15O6ReS4·H2O
563.38
C53H31BF24MoN4O2·CH2Cl2
1403.49
C54H32BF24MoN3O2
1317.57
crystal system
space group
a [ꢄ]
b [ꢄ]
c [ꢄ]
Hexagonal
¯
R3
Triclinic
P1
Monoclinic
C2/c
39.0390(4)
13.1465(1)
22.6607(2)
90
104.660(1)
90
11251.44(17)
8
Monoclinic
P21/c
19.2279(2)
13.1162(2)
22.5679(4)
90
111.555(5)
90
5293.52(14)
4
10.7117(2)
10.7117(2)
22.4874(2)
90
90
120
7.8568(3)
8.8845(4)
12.0286(4)
94.615(3)
100.239(3)
91.199(3)
823.06(6)
2
a [8]
b [8]
g [8]
V [ꢃ3]
Z
2234.53(7)
6
T [K]
100(2)
2.381
1560
100(2)
2.274
544
150(2)
1.657
55.840
293(2)
1.875
2624
Dcalc[gcmÀ3
F (000)
]
l (Ka) [ꢃ]
1.5418
1.5418
0.71073
0.71073
crystal size [mm]
m (Ka) [mmÀ1
0.08ꢄ0.11ꢄ0.17
21.747
0.01ꢄ0.03ꢄ0.10
19.468
0.15ꢄ0.17ꢄ0.25
0.454
0.12ꢄ0.15ꢄ0.17
0.378
]
collection range [8]
max/min tran. factors
reflections collected
indep reflect. [R(int)]
goodness-of-fit on F2
R, wR2 (all data)
5.16 to 66.18
0.17/0.11
877
833[0.0550]
0.996
3.75 to 73.77
0.67/0.52
3251
3173[0.0629]
1.072
1.82 to 25.36
1.04/0.95
10280
9024[0.0662]
1.099
1.85 to 25.34
0.95/0.94
9577
7496[0.0598]
1.079
0.0332, 0.0768
0.0317, 0.0761
0.0795, 0.2082
0.0788, 0.2068
0.0825, 0.2149
0.0738, 0.2051
0.0702, 0.1620
0.0506, 0.1340
R, wR2 (I>2s(I)
8
9
10
11
empirical formula
Mr
crystal system
space group
a [ꢃ]
b [ꢃ]
c [ꢃ]
a [8]
b [8]
C21H19ClMoN4O2
526.82
Monoclinic
C2/c
27.234(2)
15.2912(7)
10.3759(4)
90
92.163(7)
90
4317.9(4)
8
C21H19BrMoN4O2
535.24
Monoclinic
C2/c
25.7655(3)
15.9479(2)
19.7950(2)
90
102.709(1)
90
C22H22MoN4O5S·CH2Cl2
635.37
Monoclinic
P21/c
9.50590(1)
30.6741(4)
8.93270(1)
90
98.9030(1)
90
C44H44Mo2N8O10S2·H2O
1118.91
Triclinic
¯
P1
9.5059(4)
14.2386(4)
18.5203(6)
99.920(3)
96.675(4)
99.665(3)
2573.26(5)
2
g [8]
V [ꢃ3]
Z
7934.59(16)
16
2573.26(5)
4
T [K]
100
1.621
2128.0
100(2)
1.792
4256.0
100(2)
1.640
1288.0
100(2)
1.625
1140.0
Dcalc[gcmÀ3
F (000)
]
Chem. Eur. J. 2014, 20, 5821 – 5834
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Full Paper
Table 2. (Continued)
2
8
3
9
6
10
7
11
l (Ka) [ꢃ]
1.5418
1.5418
1.5418
1.5418
crystal size [mm]
0.02ꢄ0.06ꢄ0.09
6.357
0.12ꢄ0.13ꢄ0.83
7.985
0.03ꢄ0.17ꢄ0.31
7.204
0.13ꢄ0.14ꢄ0.18
5.934
m (Ka) [mmÀ1
]
collection range [8]
max/min tran. factors
reflections collected
indep reflect. [R(int)]
goodness-of-fit on F2
R, wR2 (all data)
3.24 to 74.10
0.74/0.69
4245
3296[0.0841]
0.987
0.0906, 0.2054
0.0726, 0.1842
3.28 to 73.99
0.70/0.10
7883
6647[0.0262]
1.000
0.0409, 0.1040
0.0327, 0.0898
2.88 to 73.88
0.80/0.26
5189
5057[0.0487]
1.008
0.0445, 0.1416
0.0416, 0.1228
3.21 to 74.09
0.47/0.43
9044
8509[0.0829]
1.017
0.0779, 0.2453
0.0735, 0.2347
R, wR2 (I>2s(I)
12
13
14
15
empirical formula
Mr
C22H20ClMoN3O2
489.80
C22H20BrMoN3O2
563.38
C22H20IMoN3O2
581.25
C22H20MoN4O5
516.36
crystal system
space group
a [ꢄ]
b [ꢄ]
c [ꢄ]
Monoclinic
P21/c
9.47600
13.2033
18.4396(1)
90
Monoclinic
P21/c
19.3963(11)
16.4011(10)
13.2390(7)
90
Monoclinic
P21/c
19.9356(4)
16.5037(5)
13.3274(3)
90
Monoclinic
P21/c
19.5695(3)
16.5757(2)
13.2932(2)
90
a [8]
b [8]
116.6300
90
5293.52(14)
4
100.345(5)
90
4143.1(4)
8
100.083(2)
90
4317.14(18)
8
100.7770(10)
90
4235.97(10)
8
g [8]
V [ꢃ3]
Z
T [K]
100(2)
1.578
992.0
100(2)
1.713
2128.0
100(2)
1.789
2272.0
100(2)
1.619
2096.0
Dcalc[gcmÀ3
F (000)
]
l (Ka) [ꢃ]
1.5418
1.5418
1.5418
1.5418
Crystal size [mm]
m (Ka) [mmÀ1
0.03ꢄ0.05ꢄ0.08
6.587
0.01ꢄ0.02ꢄ0.03
7.631
0.03ꢄ0.10ꢄ0.15
16.385
0.02ꢄ0.05ꢄ0.07
5.440
]
collection range [8]
max/min tran. factors
reflections collected
indep reflect. [R(int)]
goodness-of-fit on F2
R, wR2 (all data)
4.29 to 73.99
1.00/0.67
4174
3997[0.0224]
1.000
3.55 to 74.10
0.93/0.79
8066
3218[0.1678]
1.000
3.50 to 75.20
0.61/0.17
8659
8244[0.0520]
1.049
3.35 to 73.95
0.92/0.75
8184
7240[0.0516]
1.005
0.0227, 0.0592
0.0217, 0.0583
0.1938, 0.3378
0.0946, 0.2661
0.0607, 0.1907
0.0574, 0.1741
0.0441, 0.1111
0.0392, 0.1069
R, wR2 (I>2s(I)
16
empirical formula
Mr
C22H20MoN3O6Re·CH2Cl2
789.49
crystal system
space group
a [ꢄ]
b [ꢄ]
c [ꢄ]
Monoclinic
P21/c
11.2080(2)
17.2669(3)
13.3852(2)
90
a [8]
b [8]
101.834(2)
90
2535.35(7)
4
g [8]
V [ꢃ3]
Z
T [K]
100
2.068
1520.0
Dcalc[gcmÀ3
F (000)
]
l (Ka) [ꢃ]
1.5418
crystal size [mm]
m (Ka) [mmÀ1
0.02ꢄ0.04ꢄ0.09
15.573
]
collection range [8]
max/min tran. factors
reflections collected
indep reflect. [R(int)]
goodness-of-fit on F2
R, wR2 (all data)
3.35 to 73.72
0.70/0.48
4904
4162[0.0427]
1.001
0.0567, 0.1387
0.0461, 0.1309
R, wR2 (I>2s(I)
Chem. Eur. J. 2014, 20, 5821 – 5834
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[4] R. D. Bedford, M. Betham, C. P. Butts, S. J. Coles, M. B. Hursthouse, P. N.
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2431.
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Hursthouse, R. L. Richards, J. Chem. Soc. Dalton Trans. 1996, 4003–4010;
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Wilson, W. N. Setzer, J. Am. Chem. Soc. 1980, 102, 5068–069.
[6] D. Morales, M. Puerto, I. del Rꢁo, J. Pꢀrez, R. Lꢅpez, Chem. Eur. J. 2012,
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lection of crystal, measurement, and refinement data is given in
Table 2. Despite many attempts, only low quality crystals of 5
could be achieved. The poor diffraction data set obtained from
one of these crystals accounted for persistent NPD thermal ellip-
soids after refinement. However, the atomic connectivity in 5 could
be inferred from these data, as shown in Figure 4. This material is
available from the authors as supplementary material. CCDC-
956351 (2), 956352 (3), 956353 (6), 956354 (7), 956355 (8), 956356
(9), 956357 (10), 956358 (11), 956359 (12), 956360 (13), 956361
(14), 956362 (15), and 956363 (16) contain the supplementary crys-
tallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
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Acknowledgements
We thank Principado de Asturias (Grant IB08–104 administered
by FICYT), FEDER funds, and Ministerio de Economia y Compet-
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Keywords: host–guest systems · hydrogen bonds · metal
complexes · receptors · tris(2-pyridyl) · trithiacyclononane
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Received: September 16, 2013
Revised: January 5, 2014
Published online on March 27, 2014
Chem. Eur. J. 2014, 20, 5821 – 5834
www.chemeurj.org
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