Synthesis and properties of cryptands with a thioether bridge and π-donors - Silver(I) and copper(I)-complexes

Article abstract of DOI:10.1002/ejic.200500685

The syntheses of seven bridgehead diazabicycloalkanes are reported. The bridges are represented by either a thioether chain and two 3-hexyne units (4 and 6-8), one selenoether chain and two 3-hexyne units (5), or one dithioether chain and two 4,4′-diethyl

Full text of DOI:10.1002/ejic.200500685

FULL PAPER
DOI: 10.1002/ejic.200500685
Synthesis and Properties of Cryptands with a Thioether Bridge and π-Donors –
Silver(
I
) and Copper( )-Complexes
I
René Koschabek,[a] Rolf Gleiter,*[a] and Frank Rominger[a]
Keywords: Cage compounds / Alkynes / Silver / Copper
The syntheses of seven bridgehead diazabicycloalkanes are
reported. The bridges are represented by either a thioether
chain and two 3-hexyne units (4 and 6–8), one selenoether
chain and two 3-hexyne units (5), or one dithioether chain
and two 4,4Ј-diethylbiphenyl units (9, 10). X-ray investi-
gations reveal for 4–10 the in/in conformation at the bridge-
veal interactions between the metal ion and the nitrogen-,
chalcogen-, and π-units. In addition to the bicyclic systems
4–10 we synthesized the tripodal systems 28–33 in a one-pot
reaction. In the cases of 28 and 33 we were able to isolate
the corresponding AgI complexes. X-ray studies show an in-
teraction between the metal ion and the nitrogen atom and
head nitrogen atoms. Reactions with CuI triflate yield the en- one double bond of each of the three adjacent phenyl rings.
dohedral CuI complexes of 4–6. Endohedral complexes of 6,
7, and 10 were isolated with silver triflate. X-ray investi-
gations and spectroscopic studies on the metal complexes re-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
Introduction
After the seminal papers of Pedersen[1] on crown ethers
and Lehn et al.[2] on cryptands these types of compounds
were in the focus of chemists. Quite some time had to pass
until crown thioethers participated in this development[3]
because safe and high-yield routes to these species were
lacking. Advances in synthetic methodology[4] and safe and
general, high-yield routes[5] resulted in strong activity in this
field.[5] Reports on the corresponding podands[6] and cryp-
tands[7] with thioether bridges such as 1 are sparse, proba-
bly because a method that provides them in high yields is
still missing.
The starting point of the research reported in this manu-
script was a simple one-pot synthesis of the bridgehead di-
azabicycloalkanes 2 and 3[8,9] with alkyne and phenyl units
in the bridges (Figure 1). The two species were able to form
isolable complexes with Cu+ and Ag+ (2) and Ag+ (3),
respectively. In both cases the metal ion does not only inter-
act with the nitrogen atoms but also with the π-units. In
order to extend the variety of ligands for transition metals
it was of interest to have easy access to bicyclic ligands with
at least one thioether bridge and further alkyne or phenyl
ligands. In this paper we report a one-pot synthesis of the
bicyclic cryptands 4–10 and their complexing properties
with silver and/or copper(i) ions.
Figure 1. Bicyclic cryptands 1–10.
Results
(a) Synthesis and Structures of 4–8
To synthesize our target molecules we adopted a one-pot
synthesis developed for bridgehead diazabicycloalkanes.[10]
The preparation of 4–8 was achieved in a three-component
cyclization from an α,ω-diamine (11) and an α,ω-dibromide
[a] Organisch-Chemisches Institut, Universität Heidelberg,
Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Fax: +49-6221-544205
E-mail: Rolf.Gleiter@urz.uni-heidelberg.de
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R. Koschabek, R. Gleiter, F. Rominger
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(12) as shown in Scheme 1. The components were heated in
acetonitrile under reflux. The yields varied between 33% (5)
and 53% (7). From the starting materials 1,5-diamino-3-
thiapentane (13),[11] 1,5-diamino-3-selenapentane (14),[12]
1,8-diamino-3,6-dithiaoctane (15),[13] as well as 1,6-di-
bromohex-3-yne (16)[14] were prepared according to litera-
ture procedures.
Scheme 3.
With regard to the silver(i) complexes of 3, 9, and 10 we
also prepared the tripodal systems 28–33 listed in Figure 2.
The synthesis follows that given in Scheme 1 by applying a
one-pot reaction of (2-bromoethyl)benzene[15] or 4-(2-bro-
moethyl)biphenyl[16] with the corresponding amines such as
(2-aminoethyl)benzene which was commercially available,
4-(2-aminoethyl)biphenyl,[17] or 1-aminobut-3-yne.[18,19]
The components were heated in acetonitrile under reflux
with an excess of potassium carbonate.
Scheme 1.
The synthesis of 1,9-diamino-3,7-dithianonane (17) and
1,10-diamino-3,8-dithiadecane (18) followed those pro-
cedures[13] used for 13–15 and is summarized in Scheme 2.
The dianions of the α,ω-dithiols 19 and 20 were reacted
with N-(2-bromoethyl)phthalimide (21) to the α,ω-diphthal-
imidodithianes 22 and 23. The protecting groups were re-
moved by heating of 22 and 23, respectively, with hydrazine
in ethanol to afford 17 and 18 in good yields.
Figure 2. Tripodal systems 28–33.
Scheme 2.
The preparation of 4,4Ј-bis(2-hydroxyethyl)biphenyl (25)
(Scheme 3) was described in the literature from biphenyl
and ethylene oxide under Lewis acid catalysis.[15] This pro-
(b) Spectroscopic and Structural Properties
In Table 1 we list the 13C chemical shift of the sp centers
cedure gave us a mixture of the 4-(2-hydroxyethyl)biphenyl of 4–8 as well as the wave numbers for the C,C stretching
and 25 which was difficult to separate. Therefore, a different mode of the triple bonds derived by Raman spectroscopy.
path as shown in Scheme 3 was used. The starting point It is seen that the δ values for the sp centers vary only
was the commercially available 4,4Ј-dibromobiphenyl (24), slightly between 79.5 and 81 ppm indicating hardly any
which was treated with an excess of n-butyllithium and eth- strain in these systems. This view is supported by the wave
ylene oxide to afford 25 in 92% yield. The diol 25 was con- numbers for the stretching vibration of the triple bonds. For
verted via the dimesylate 26 into the dibromide 27 in a 7 and 8 we encountered dynamic processes in the 1H NMR
straight forward way (Scheme 3).
spectra which led to a line broadening at room temperature.
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Synthesis and Properties of Cryptands with a Thioether Bridge and π-Donors
FULL PAPER
Table 1. Comparison of the chemical shift of the sp carbon atoms (c) Formation of Metal Complexes
(δ) and the alkyne wave numbers of 4–8.
The reactions of 28 and 33 with silver triflate afforded
the 1:1 complexes. For 29, 30, and 32 the corresponding 1:1
silver complexed ions were only detected in the mass spec-
trum (FAB+). In Figure 4 we show the molecular structures
of 28·Ag+ and 33·Ag+ in a front and side view. In 28·Ag+
the distance between the nitrogen center and silver atom
amounts to 2.41 Å. This distance is closer than that found
in the silver complex of 3 (2.47 Å).[10] The interaction be-
tween the silver ion and the aromatic rings is evident from
the change of the NMR shifts. In the uncomplexed species
(28) the protons at the sp3 centers (positions 1 and 2 in
28) show two close lying multiplets at 2.75–2.81 and 2.84–
2.90 ppm. Similarly, the aromatic protons resonate at 7.21–
7.24 and 7.32 ppm. In the silver complex the CH2 protons
give rise to two pronounced triplets at δ = 2.70 and
2.94 ppm. In the aromatic region two protons of each C6H5
ring give rise to a doublet at δ = 6.84 ppm. These spectro-
scopic data are in line with the observation that the silver
ion shows a much closer contact with the ortho carbon
atoms (position 3 in 28) of the benzene rings as compared
to the other sp2 centers. For the three phenyl rings in
28·Ag+ we observe a tilting of the aromatic rings in a con-
rotatory fashion parallel to the C3 axis. This brings one car-
bon atom per ring close to the metal center. The distance
between these carbon atoms of the phenyl rings and the
metal ion (average 2.47 Å, see Table 3) are similar to that
found for various silver complexes of [2.2.2]- and [2.2.1]cy-
clophanes.[20–25] For 33·Ag+ we observe in the 1H NMR
spectrum two triplets at δ = 2.83 and 2.99 ppm for the hy-
drogen atoms at centers 1 and 2 (see Figure 2). Six of the
aromatic hydrogen atoms are shifted towards higher field
due to the complexation and give rise to a doublet at δ =
6.96 ppm. The other 21 aromatic hydrogen atoms show up
at 7.35–7.44 ppm. These results suggest a similar situation
for the silver atom as in 28·Ag+. Indeed, the molecular
structure of 33·Ag+ reveals that the metal ion is situated
close to the nitrogen atom. The N–Ag+ distance amounts
to 2.37 Å (Table 3). The view along the N···Ag axis of
33·Ag+ shows that the aromatic rings are twisted in a con-
rotatory way similar to that found in 28·Ag+. This orienta-
tion allows a closer interaction between the metal atom and
C3 than to the other sp2 centers (average 2.43 Å, Table 3).
For 4–10 we infer from the downfield shift of the signals
Compound
4
5
6
7
8
δ(sp) [ppm]
80.6[b] 80.6[b] 79.5[a] 79.9[a] 80.2[a]
2228
2291
ν [cm–1][c]
2227
2289
2236
2300
2231
2293
2237
2297
˜
[a] CDCl3. [b] CD2Cl2. [c] Raman spectroscopic data.
For 4–10 we grew single crystals which allowed a com-
parison of the geometrical parameters. In Figure 3 we show
the structures of 4, 6, 7, and 10. In all cases we find the in/
in conformation at the bridgehead positions. A single nearly
planar nitrogen atom is only seen in 4. The heteroatoms of
the bridges point outwards and do not seem very well suited
for the complexation of a cation in the inside of the cages.
In Table 2 we list the distances between the bridgeheads
(N···N), the sum of the bonding angles (ΣωN), and the dis-
tance between the centers of the π-systems, either triple
bonds (4–8) or aromatic rings (9, 10). In the latter case each
biphenyl ring provides two centers. It is interesting to note
that the N···N distance of 4 is larger than that of 5. We
ascribe this difference to the larger C–S–C angle (99°) of 4
as compared to the C–Se–C angle (97°) of 5. In all cases
the triple bonds are not oriented parallel to each other. In
the biphenyl-bridged cages the N···N distances amount to
nearly 10 Å.
1
for the aliphatic hydrogen atoms in the H NMR spectra
Figure 3. Molecular structures of 4 (a), 6 (b), 7 (c) and 10 (d).
Table 2. Selected distances and angles (degrees) of 4–10.
and from the mass spectrometric data the inclusion of silver
and/or copper(i) ions into the cavities of these species. In
all cases except for 9 this result was confirmed by the isola-
tion of single crystals which allowed a detailed study of the
molecular structure. For 4 and 5 we were able to isolate
only complexes with copper(i) triflate. The reaction of 6
with silver or copper triflate gave complexes with one metal
ion in the cavity. For all the other cryptates, only silver
complexes could be characterized. In the case of 10 even
two silver ions were incorporated in the cavity. In Figure 5
we show the molecular structures of 4·Cu(CF3SO3),
8·Ag(CF3SO3), and 10·2[Ag(CF3SO3)2].
Compound
4
5
6[d]
4.87 4.79 4.90 5.20 9.79 9.94
(329)[c] 342 335 338 343 328 328
7
8
9
10
N···N [Å]
4.72 4.31
344
357
[a]
(ΣωN
)
343
342 336 342 344 343 330
3.87 4.17 3.92 3.77
π···π
3.84 4.30
(sp)(Å)[b]
[a] Sum of the C–N–C angles at nitrogen centers. [b] Transannular
distances between centers of π-systems. [c] Unreliable due to partial
disorder. [d] Two independent molecules in the unit cell.
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Figure 4. Molecular structures of 28·Ag+ (top) and 33·Ag+ in a
front view (a) and a view along the N–Ag axis (b).
Table 3. Selected distances [Å] of AgI triflates of 28 and 33.
28·Ag+
33·Ag+
N···Ag
π···Ag
π···π
2.409
2.371
2.47[a,b]
3.72[a,b]
2.43[a,b]
3.72[a,b]
Figure 5. Molecular structures of 4·Cu+ (top), 8·Ag+ and 10·2(Ag+)
(bottom).
[a] Average value. [b] Closest atom of C6 units.
In Table 4 we collected the most relevant distances and value 2.18 Å)[26] but comparable to those reported for
angles of the metal complexes of 4–8 and 10. The copper 2·Cu+ (2.11 Å).[9] The distance Cu–S (2.52 Å) is longer than
complex of 4 shows a considerable change in the conforma- those reported in other thioether-CuI complexes (2.25–
tion of the ligand. The N···N distance is substantially short- 2.30 Å).[27]
ened from 4.72 Å (free ligand) to 4.20 Å (complex) (see Fig-
The molecular structure of 5·Cu+ is isomorphous to that
ure 3 and Figure 5). As a result of this change the triple of 4·Cu+. The N···N distance in the complex (4.21 Å) is
bonds are oriented almost parallel and the chalcogen center about as long as that in 4·Cu+ (4.20 Å). The same holds for
of the bridge is turned towards the metal. This change al- the N–Cu distances and the N–M–N angle, 160.5° in 4·Cu+
lows almost equal distances to both nitrogen centers (2.10 and 161.6° for 5·Cu+. Also both triple bonds are almost
and 2.16 Å) but close contact to only one triple bond oriented parallel to each other in contrast to the free ligand.
(2.13 Å), whereas the distance to the other (2.71 Å) is con- The selenium atom is bent sideways to interact with the
siderably longer. The copper–nitrogen distances are ex- copper ion (Cu–Se = 2.62 Å). The complex shows one close
panded with regard to copper(i) amine complexes (average contact to one triple bond (2.16 Å) only.
Table 4. Selected distances [Å] and angles (degrees) of AgI or CuI triflates of 4–8 and 10.
Compound
4·Cu+
5·Cu+
6·Ag+
6·Cu+
7·Ag+
8·Ag+
10·2(Ag+)
N···N
N···M
4.200
2.101
2.160
2.520
4.209
2.098
2.166
2.620
4.830
2.435
2.450
2.757
2.876
2.609
2.664
197.3
4.286
5.077
2.150
3.150
2.275
2.562
2.093
3.015
214.0
3.751
5.129
2.646
2.678
2.754
2.773
2.640
2.721
211.6
4.011
2206
4.739
2.368
2.468
2.574
5.043
2.656
2.745
203.2
4.304
2204
9.951
2.429
2.444
2.500
X···M[a]
M···π
2.564
2.134
2.705
160.5
4.335
2.157
2.733
161.6
4.363
2.53[b,d,e]
2.47[c,d,e]
N···M···N[f]
π···π
3.611[d,e]
ν
[cm–1][g]
˜
(CϵC)
2281
2266
[a] X = S for 4, 7–9, 11; X = Se for 5; X = O for 6. [b] Average value for Ag1. [c] Average value for Ag2. [d] Average value. [e] Closest
atom of C6 units. [f] For comparison with the other structures we define the N–metal–N angle as greater than 180° if the metal deviates
from the N···N axis in the direction of the thioether bridge and smaller than 180° if it deviates towards the π-system. [g] Raman spectro-
scopic data.
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Synthesis and Properties of Cryptands with a Thioether Bridge and π-Donors
FULL PAPER
The molecular structures of 6·Ag+ and 6·Cu+ are shown of the 3,7-dithiononane bridge in so far as the sulfur centers
in Figure 6. In the case of 6·Ag+ we are not dealing with a are turned inward to interact with the metal ion. The N···N
purely endohedral complex between ligand and metal. The distance is even increased as compared to the free ligand.
unit cell does not only show the endohedral metal ion but The silver ion is shifted considerably out of the N···N axis
also exohedral metal ions between the thioether groups (see towards the sulfur atoms (N–Ag–N angle 211.6°). In line
Figure 6) that lead to a coordination polymer. In the en- with this, the distances between the triple bonds and the
dohedral complex the metal ion deviates from the N···N silver ion amount to 2.64 and 2.72 Å. These values are
axis in the direction of the thioether bridge N···Ag···N about 0.2 Å larger than those reported for 2·Ag+.[9] In the
(197.3°). This deviation is due to a interaction between the case of 7·Ag+ it was possible to measure the wave number
silver ion and the sulfur centers. The Ag···S distances found for the stretching vibration of the triple bond (ν = 2281 and
˜
(Table 4; 2.76 Å and 2.88 Å) compare well with other thio- 2206 cm–1). These values are shifted towards lower energy
ether–silver distances.[28,29] The distances between the exo- as compared to the free ligand (ν = 2293 and 2231 cm–1)
˜
hedral silver centers and the thioether groups amount to which is evidence for an interaction between the metal and
2.49 Å and 2.50 Å. The average Ag···N distance (2.45 Å) is the triple bonds. The distances between the sulfur centers
longer than the one reported for 2·Ag (2.31 Å).[8] The dis- and the metal atom amount to 2.75 and 2.77 Å. These val-
tances between the endohedral silver ions and the triple ues are close to those reported for thioether-silver distances
bonds (2.61, 2.66 Å) are still within the reach of a weak (2.6–2.8 Å).[28,29]
metal–π-bond. Raman studies on 6·Ag+ failed due to a fast
The molecular structure of 8·Ag+ (Figure 5) is quite dif-
decomposition of the complex during the Raman experi- ferent from that of 7·Ag+ in so far as only one sulfur atom
ment. Our studies show that the large silver ion prefers a of the flexible dithia bridge interacts with the silver center.
coordination number of 6.
The other sulfur atom points outwards. The Ag–S distance
(2.57 Å) is rather close compared to the other values. The
N···N distance is shortened by about 0.5 Å compared to the
uncomplexed system. The N–Ag distances (2.37 and
2.47 Å) are much shorter than for 7·Ag+ (see Table 4) and
the two triple bonds are oriented parallel to each other. The
interaction between the silver ion and the triple bonds is
evident not only from the distances (2.66 and 2.75 Å) but
also in the lowering of the wave numbers for the stretching
vibration (ν = 2266 and 2204 cm–1) as compared to 8 (ν =
˜
˜
2297 and 2237 cm–1). The reaction of 9 with silver(i) triflate
afforded a 1:1 complex as evidenced by HR-FAB+ data.
1
The comparison between the H NMR spectroscopic data
of 9·Ag+ with those of 9 shows a downfield shift of the
signals for the protons.
The reaction of 10 with silver(i) triflate afforded single
crystals which could be investigated by means of the X-ray
technique. It turned out that the cavity of 10 is large enough
to house two silver ions (Figure 5). The incorporation of
the two metal ions causes only a small change in the length
of the cavity but a large one in the conformation of the
thioether chain. The sulfur atoms are now turned inwards
(see also Figure 3). The distance between the two silver ions
in 10·2(Ag+) was found to be 5.18 Å. This value is clearly
larger than the sum of the van der Waals radii of Ag+ (3.1–
Figure 6. Molecular structure of 6·Ag+ (top) and 6·Cu+ (bottom)
in a front view (a) and a view along the N–N axis (b). The hydrogen
atoms are omitted for the sake of clarity.
The structure of 6·Cu+ (Figure 6) is remarkably different 3.2 Å).[30,31] The average distance to the nitrogen atoms was
from that of 6·Ag+. The position of the metal is shifted found to be 2.44 Å which compares well with those re-
towards one nitrogen center and one triple bond. The dis- corded for 6·Ag+ and 8·Ag+ (Table 4). A closer look at the
tance to the nitrogen center amounts to 2.15 Å and to the Ag···phenyl interaction reveals a situation very similar to
triple bond to 2.09 Å. The distances to the second nitrogen that encountered for 28.Ag+and 33.Ag+ as well as for vari-
center and to the second triple bond in 6·Cu+ exceed 3 Å ous [2.2.2] and [2.2.1]cyclophanes.[20–25] One carbon atom
(Table 4). As a consequence both triple bonds in 6·Cu+ are per ring is much closer to the silver ion than the other sp2
not oriented parallel (Figure 6). Furthermore, the metal ion centers. For three phenyl rings this is a ortho carbon
coordinates to both thioether groups (2.28, 2.56 Å). This (average distance 2.48 Å), only in one case is the silver ion
establishes a coordination number of 4 for the metal in closest to the ipso-carbon (2.50 Å). This coordination does
6·Cu+.
not affect the planarity of the aromatic rings. The Ag–S
The inclusion of AgI in the cavity of 7 does not change distance of 2.50 Å is similar to that found in 8·Ag+ and
the tilting of the triple bonds, but changes the conformation shorter than in 6·Ag+ and 7·Ag+ (see Figure 6).
Eur. J. Inorg. Chem. 2006, 609–620
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R. Koschabek, R. Gleiter, F. Rominger
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ethyl)biphenyl[17]
according to literature procedures. 2-Aminoethylbenzene and
,
and 1-aminobut-3-yne[18,19] were prepared
Concluding Remarks
Our main goal to find a simple procedure for the prepa-
ration of N-bridgehead diazabicyclo-cages with one thio-
ether bridge and π units in the other two was achieved. Like
in crown thioethers the sulfur atoms adopt the exodentate
orientation. However, when a metal ion was in the cavity
this unfavorable position was changed to a more favorable
one, mostly to the endodentate one. The prepared cage sys-
tems afforded endohedral complexes with silver or copper
ions. It could be shown that the metal ions try to interact
with a maximum of n-donors (N, S, Se) and π-donors (triple
bonds or phenyl rings).
4,4Јdibromobiphenyl were commercially available.
X-ray Crystallographic Study: Data were collected with a Bruker
Smart CCD diffractometer at 200 K for 4, 6, 7, 4·Cu+, 5·Cu+,
6·Cu+, 6·Ag+, 7·Ag+, 10·2(Ag+), 28·Ag+, 33·Ag+, and with a
Bruker APEX diffractometer at 100 K for 5, 8, 9, 10, and 8·Ag+.
Mo-Kα radiation was used in all cases and the intensities were cor-
rected for Lorentz, polarization, and absorption effects. Relevant
crystal and data collection parameters are given in Tables 5, 6, 7,
8 and 9. The structures were solved by direct methods and refined
against F2 with a full-matrix least square algorithm by using the
SHELXTL software package.[32] Hydrogen atoms were refined iso-
tropically for 8, in all other cases they were considered at calculated
positions and refined using appropriate riding models. In 10,
10·2(Ag+), and 6·Ag+ some solvent molecules or anions had to be
treated as disordered, in 4·Cu+ and 5·Cu+ on one side of the cage
the three methylene groups next to the nitrogen atom occur in two
alternative positions, in 9 an ethylene unit of the thioether bridge
is affected by disorder. In 4·Cu+ and 5·Cu+ the copper position is
not fully occupied. The charge balance is maintained by partial
replacement of the metal ion by a proton, which could be refined
isotropically with an occupation of about 30% in both cases.
CCDC-279304 (for 4), -279305 (for 5), -279306 (for 6), -279307 (for
7), -279308 (for 8), -279309 (for 9), -279310 (for 10), -279311 (for
4·Cu+), -279312 (for 5·Cu+), -279313 (for 6·Cu+), -279314 (for
6·Ag+), -279315 (for 7·Ag+), -279316 (for 8·Ag+), -279317 [for
10·2(Ag+)], -279318 (for 28·Ag+), and -279319 (for 33·Ag+) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Experimental Section
General Methods: All melting points are uncorrected. Elemental
analyses were carried out by the Mikroanalytisches Laboratorium
der Universität Heidelberg. UV/Vis absorption data were recorded
with a Hewlett-Packard HP 8452A Diode Array-spectrometer, IR
spectra were recorded with a Bruker Vector 22 FT-IR instrument.
The NMR spectra were measured with a Bruker WH 300 or Av-
ance 500 spectrometer (1H NMR at 300 or 500 MHz and 13C NMR
at 75 or 125 MHz), using the solvent as an internal standard (δ).
FAB mass spectra refer to data from a JEOL JMS-700 instrument.
As matrix for the FAB experiments, m-nitrobenzyl alcohol was
used. All reactions were carried out in dried glassware under argon
using dried and oxygen-free solvents. Starting materials were pre-
pared according to literature procedures. From the starting materi-
als 1,5-diamino-3-thiapentane,[11] 1,5-diamino-3-selenapentane,[12]
1,8-diamino-3,6-dithiaoctane,[13] 1,6-dibromohex-3-yne,[14] (2-bro-
moethyl)benzene,[15] 4-(2-bromoethyl)biphenyl,[16] 4-(2-amino-
1,9-Diphthalimido-3,7-dithiononane (22): To a solution of 1,3-pro-
pane dithiole (4.2 g, 39 mmol) in dry toluene (250 mL) cooled to
–30 °C, was added dropwise nBuLi in hexane (51 mL). After 30 min
Table 5. Crystal data and structural refinement for 4–7.
4
5
6
7
Empirical formula
Formula weight [g/mol]
C16H24N2S
276.43
C16H24N2Se
323.33
C18H28N2S2
336.54
C19H30N2S2
350.57
Temperature [K]
Crystal system
Space group
200(2)
monoclinic
P21/c
200(2)
200(2)
200(2)
monoclinic
P21/c
triclinic
triclinic
¯
¯
P1
P1
Z
a
b
c
4
2
4
4
13.9024(4)
12.1766(4)
9.4685(3)
90
107.952(1)
90
1524.83(8)
1.204
0.202
0.97 / 0.95
polyhedron
0.24×0.16×0.14
1.54 to 26.36
14360
3112 (0.0428)
2310
8.7619(9)
9.3813(10)
10.0202(11)
74.661(2)
79.285(2)
84.656(2)
779.61(14)
1.377
9.5652(2)
13.0918(3)
15.9324(3)
102.849 (1)
93.051(1)
100.820(1)
1901.9(7)
1.176
13.6724(2)
9.6549(1)
15.3467(2)
90
102.995(1)
90
1973.97(4)
1.180
0.272
0.97 / 0.92
polyhedron
0.30×0.20×0.10
1.53 to 27.49
19923
4535 (0.0356)
3568
α
β
γ
V [Å3]
Dcalcd. [g/cm3]
Abs. coeff. [mm–1]
Max. / min. transmission
Crystal shape
2.398
0.279
0.80 / 0.67
polyhedron
0.18×0.11×0.10
2.14 to 28.38
8130
3870 (0.0344)
2878
0.95 / 0.73
polyhedron
0.37×0.29×0.24
1.84 to 27.44
19809
8624 (0.0255)
6308
Crystal size [mm3]
Θ range [°]
Reflections collected
Indep. reflections [R(int)]
Obsd. reflections [I Ͼ 2σ(I)]
Data / restraints / parameters 3112 / 0 / 172
3870 / 74 / 191
1.04
8624 / 0 / 397
1.07
4535 / 0 / 208
1.04
GOF(F2)
1.02
R(F)
0.037
0.083
0.18 and –0.25
0.045
0.103
0.60 and –0.51
0.039
0.097
0.39 and –0.44
0.033
0.078
0.22 and –0.23
Rw(F2)
(Δρ)max, (Δρ)min [e·Å–3]
614
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 609–620

Synthesis and Properties of Cryptands with a Thioether Bridge and π-Donors
Table 6. Crystal data and structural refinement for 8–10.
FULL PAPER
8
9
10
Empirical formula
Formula weight
C20H32N2S2
364.60
C39H46N2S2
606.90
C40H48N2S2·1.5 CH2Cl2
748.31
Temperature [K]
Crystal system
Space group
100(2)
monoclinic
P21/n
200(2)
monoclinic
P21/c
100(2)
orthorhombic
P21212
Z
a
b
c
4
4
4
7.2802(6)
14.149(1)
19.870(2)
90
14.392(2)
16.697(2)
15.492(2)
90
14.648(2)
29.035(4)
8.950(1)
90
α
β
γ
93.587(2)
90
2042.7(3)
1.186
117.506(3)
90
3301.9(7)
1.22
90
90
3806.6(9)
1.306
0.383
0.98 / 0.89
irregular
0.32×0.26×0.06
1.56 to 28.32
39939
9449 (0.1470)
6525
V [Å3]
Dcalcd. [g/cm3]
Abs. coeff. [mm–1]
Max. / min. transmission
Crystal shape
0.265
0.19
0.98 / 0.92
irregular
0.30×0.07×0.07
1.77 to 24.71
15874
3486 (0.0789)
2937
0.99 / 0.93
irregular
0.38×0.07×0.04
2.01 to 21.97
19853
4021 (0.0725)
3227
Crystal size [mm3]
Θ range [°]
Reflections collected
Indep. reflections [R(int)]
Obsd. reflections [I Ͼ 2σ(I)]
Data / restraints / parameters
GOF(F2)
3486 / 0 / 345
1.25
4021 / 0 / 574
1.19
9449 / 12 / 436
1.10
R(F)
0.071
0.122
0.37 and –0.33
0.058
0.104
0.20 and –0.20
0.134
0.311
0.83 and –0.71
Rw(F2)
(Δρ)max, (Δρ)min [e·Å–3]
Table 7. Crystal data and structural refinement for 6·Ag+, 7·Ag+, and 8·Ag+.
6·Ag+
7·Ag+
8·Ag+
Empirical formula
Formula weight
C20H28Ag2F6N2O6S4
850.42
C20H30AgF3N2O3S3
607.51
C21H32AgF3N2O3S3
621.54
Temperature [K]
Crystal system
Space group
200(2)
monoclinic
P21/c
200(2)
monoclinic
P21/c
200(2)
triclinic
¯
P1
Z
a
b
c
4
4
2
11.3822(1)
13.6579(1)
19.1305(1)
90
93.208(1)
90
2969.31(4)
1.902
1.676
0.7638 / 0.5538
polyhedron
0.40×0.21×0.17
1.79 to 27.48
30222
10.5359(1)
15.1706(3)
15.0937(3)
90
93.805(1)
90
2407.20(7)
1.676
1.146
0.89 / 0.80
polyhedron
0.20×0.12×0.10
1.91 to 27.46
16273
9.846(1)
9.918(1)
13.103(1)
96.383(2)
106.648(2)
92.734(29)
1214.0(2)
1.700
α
β
γ
V [Å3]
Dcalcd. [g/cm3]
Abs. coeff. [mm–1]
Max. / min. transmission
Crystal shape
Crystal size [mm3]
Θ range [°]
1.138
0.97 / 0.83
irregular
0.17×0.17×0.03
1.64 to 28.36
12638
Reflections collected
Indep. reflections [R(int)]
6807
5420
5974
0.0253
5876
6807 / 91 / 434
1.07
0.0422
3979
5420 / 0 / 289
1.03
0.0314
4803
5974 / 0 / 426
1.00
Obsd. reflections [I Ͼ 2σ(I)]
Data / restraints / parameters
GOF(F2)
R(F)
0.025
0.061
0.89 and –0.82
0.032
0.068
0.52 and –0.77
0.034
0.068
1.06 and –0.89
Rw(F2)
(Δρ)max, (Δρ)min [e·Å–3]
of mechanical stirring at –30 °C a solution of N-2-bromoethyl-
phthalimid (20 g, 78.7 mmol) in dry toluene (250 mL) was added
dropwise over a period of 1 h so that the temperature was main-
tained below 0 °C. After mechanical stirring overnight at room
temperature the suspension was finally refluxed for 1 h. To workup
water (100 mL) was added and the organic layer was washed a fur-
ther 2× with water. After drying with magnesium sulfate and re-
moval of the solvent, pure 22 (13.2 g, 75%) was obtained by
crystallization from acetone as a white solid, m.p. 106 °C. 1H NMR
3
3
(500 MHz, C6D6): δ = 1.59 (q, J = 7.1 Hz, 2 H, CH2), 2.36 (t, J
Eur. J. Inorg. Chem. 2006, 609–620
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615

R. Koschabek, R. Gleiter, F. Rominger
FULL PAPER
Table 8. Crystal data and structural refinement for 10·2(Ag+), 28·Ag+, and 33·Ag+.
10·2(Ag+)
28·Ag+
33·Ag+
Empirical formula
Formula weight
C42H48Ag2F6N2O6.5S4
1142.80
C26H29AgCl2F3NO3S
671.33
C44H41AgCl2F3NO3S
899.61
Temperature [K]
Crystal system
Space group
200(2)
monoclinic
C2
200(2)
orthorhombic
P212121
200(2)
monoclinic
Cc
Z
a
b
c
4
4
4
49.5268(10)
8.3859(2)
11.1401(1)
90
13.6160(2)
13.8719(2)
14.8042(3)
90
30.3342(5)
9.0243(2)
15.2387(3)
90
α
β
γ
102.566(1)
90
4516.32(15)
1.681
90
90
103.637(1)
90
4053.92(14)
1.474
V [Å3]
2796.21(8)
1.595
1.035
0.95 / 0.62
polyhedron
0.52×0.28×0.05
2.01 to 24.09
22138
4431 (0.0493)
3867
Dcalcd. [g/cm3]
Abs. coeff. [mm–1]
Max. / min. transmission
Crystal shape
Crystal size [mm3]
Θ range [°]
1.127
0.735
0.96 / 0.81
polyhedron
0.20×0.04×0.04
0.84 to 22.99
16130
6290 (0.0591)
4918
0.96 / 0.77
polyhedron
0.38×0.24×0.06
1.38 to 25.34
17041
7344 (0.0484)
5788
Reflections collected
Indep. reflections [R(int)]
Obsd. reflections [lϾ2σ(l)]
Data / restraints / parameters
GOF (F2)
6290 / 264 / 637
1.04
4431 / 0 / 334
1.02
7344 / 2 / 496
0.99
R (F)
0.042
0.076
0.63 and –0.44
0.031
0.064
0.49 and –0.36
0.040
0.062
0.42 and –0.47
Rw(F2)
(Δρ)max, (Δρ)min [e·Å–3]
Table 9. Crystal data and structural refinement for 4·Cu+, 5·Cu+, and 6·Cu+.
4·Cu+
5·Cu+
6·Cu+
Empirical formula
Formula weight
C17H24CuF3N2O3S2
489.04
C17H24CuF3N2O3SSe
535.94
C19H28CuF3N2O3S3
549.15
Temperature [K]
Crystal system
Space group
200(2)
monoclinic
P21/c
201(2)
monoclinic
P21/c
200(2)
monoclinic
P21
Z
a
b
c
4
4
2
9.7328(1)
10.5468(2)
18.9631(3)
90
9.7680(1)
10.6242(2)
18.9135(1)
90
9.0166(1)
9.7697(1)
13.6670(2)
90
α
β
γ
93.159(1)
90
1943.60(5)
1.671
92.897(1)
90
1960.28
1.816
3.127
0.71 / 0.41
polyhedron
0.36×0.24×0.12
2.09 to 27.48
19922
4494 (0.0298)
3961
108.306(1)
90
1142.99(2)
1.596
V [Å3]
Dcalcd. [g/cm3]
Abs. coeff. [mm–1]
Max. / min. transmission
Crystal shape
1.388
1.278
0.77 / 0.67
polyhedron
0.32×0.30×0.20
2.10 to 27.47
19753
4451 (0.0283)
3799
0.88 / 0.57
polyhedron
0.49×0.29×0.10
1.57 to 27.48
11787
5192 (0.0227)
4853
Crystal size [mm3]
Θ range [°]
Reflections collected
Indep. reflections [R(int)]
Obsd. reflections [I Ͼ 2σ(I)]
Data / restraints / parameters
GOF (F2)
4451 / 92 / 285
1.04
4494 / 92 / 285
1.05
5192 / 1 / 280
1.04
R (F)
0.027
0.068
0.34 and –0.42
0.024
0.055
0.28 and –0.35
0.025
0.064
0.35 and –0.41
Rw(F2)
(Δρ)max, (Δρ)min [e·Å–3]
3
3
= 7.2 Hz, 4 H, CH2), 2.55 (t, J = 7.0 Hz, 4 H, CH2), 3.60 (t, J = 2929, 2850, 1773, 1714, 1465, 1449, 1442, 1419 cm–1. UV/Vis
7.0 Hz, 4 H, CH2), 6.81–6.85 (m, 4 H, CarH), 7.36–7.41 (m, 4 H,
(CH2Cl2): λmax (lg ε) = 294 (4.5) nm. HRMS (FAB) calcd. for
CarH) ppm. 13C NMR (125 MHz, C6D6): δ = 29.2 (s, CH2), 30.0 C23H22N2O4S2, 455.1099; found 455.1073. C23H22N2O4S2 (455.11):
(s, CH2), 30.4 (s, CH2), 37.2 (s, CH2), 123.1 (t, Car), 132.6 (q, Car), calcd. C 60.77, H 4.88, N 6.16, S 14.11; found C 60.49, H 4.96, N
133.6 (t, C ), 167.9 (q, CO) ppm. IR (KBr): ν = 3459, 3053, 2964, 6.13, S 14.08.
˜
ar
616
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Eur. J. Inorg. Chem. 2006, 609–620

Synthesis and Properties of Cryptands with a Thioether Bridge and π-Donors
FULL PAPER
1,10-Diphthalimido-3,8-dithiodecane (23): To a solution of 1,3-pro-
panedithiol (4.8 g, 39 mmol) in dry toluene (250 mL), cooled to
–30 °C was added dropwise nBuLi in hexane (51 mL). After 30 min
of mechanical stirring at –30 °C a solution of N-2-bromoethyl-
phthalimide (20 g, 78.7 mmol) in dry toluene (250 mL) was added
dropwise over a period of 1 h so that the temperature was main-
tained below 0 °C. After mechanical stirring overnight at room
temperature the suspension was finally refluxed for 1 h. To workup
water (100 mL) was added and the organic layer was washed fur-
ther 2× with water. After drying with magnesium sulfate and re-
moval of the solvent, pure 23 (12.1 g, 66%) was obtained by
crystallization from acetone as a white solid, m.p. 100 °C. 1H NMR
added a solution of 10 m nBuLi in hexane (42 mL, 420 mmol). The
mixture was heated at reflux for 12 h. To this suspension dry THF
(500 mL) was added and cooled to –40 °C. Subsequently ethylene
oxide (31 mL, 617 mmol) was added. After 36 h of mechanical stir-
ring at –35 °C water (500 mL) was added. Subsequently the mixture
was stirred for a further 30 min. The white precipitate was then
filtered off and dried with silica gel and finally crystallized from
1
hexane to yield 25 (21 g, 92%), m.p. 183 °C. H NMR (500 MHz,
3
3
CD2Cl2): δ = 1.45 (t, J = 5.8 Hz, 2 H, OH), 2.87 (t, J = 6.6 Hz,
3
3
4 H, CH2), 3.85 (t, J = 6.6 Hz, 4 H, CH2), 7.29 (d, J = 8.1 Hz, 4
H, CarH), 7.53 (d, 3J = 8.1 Hz, 4 H, CarH) ppm. 13C NMR
(125 MHz, CD2Cl2): δ = 38.8 (s, CH2), 63.44 (s, CH2), 126.9 (t,
(500 MHz, C6D6): δ = 1.39 (s, 4 H, CH2), 2.27 (s, 4 H, CH2), 2.57 C ), 129.4 (t, C ), 137.9 (q, C ), 138.9 (q, C ) ppm. IR (KBr): ν
˜
ar
ar
ar
ar
3
3
(t, J = 7.1 Hz, 4 H, CH2), 3.62 (t, J = 7.0 Hz, 4 H, CH2), 6.82–
= 3420, 3030, 2942, 2878, 2049, 1911, 1633, 1500, 1476 cm–1. UV/
6.86 (m, 4 H, CarH), 7.38–7.42 (m, 4 H, CarH) ppm. 13C NMR Vis (CH2Cl2): λmax (lg ε) = 258 (4.3) nm. HRMS (FAB) calcd. for
(125 MHz, C6D6): δ = 28.6 (s, CH2), 30.1 (s, CH2), 31.2 (s, CH2), C16H18O2 242.1307; found 242.1323. C16H18O2 (242.13): calcd. C
37.2 (s, CH2), 123.1 (t, Car), 132.6 (q, Car), 133.6 (t, Car), 167.9 (q,
79.31, H 7.49; found C 79.17, H 7.31.
CO) ppm. IR (KBr): ν = 3460, 3102, 3048, 3018, 2945, 2923, 2865,
˜
4,4Ј-Bis(2-methylsulfonylethyl)biphenyl (26): To a solution of 25
(21.4 g, 88.3 mmol) in dichloromethane (350 mL) was added by
cooling to –20 °C triethylamine (28.8 g, 285 mmol). Subsequently
methanesulfonyl chloride (24.5 g, 213.8 mmol) was added to the
mixture at such a rate that the temperature was maintained below
–10 °C. After the addition was completed the suspension was
stirred for 2 h. For workup water (100 mL) was added and the or-
ganic layer was washed with 10% hydrogen chloride solution, fol-
lowed by saturated sodium hydrogen carbonate solution and again
by saturated sodium chloride solution and water. The organic layer
was dried with magnesium sulfate and the solvent evaporated. Puri-
fication by column chromatography (alumina; cyclohexane/ethyl
acetate, 4:1) afforded 26 (29.0 g, 82%) as a white solid, m.p. 82 °C.
1774, 1699, 1613, 1578, 1464, 1433, 1417 cm–1. UV/Vis (CH2Cl2):
λmax (lg ε) = 294 (3.5) nm. HRMS (FAB) calcd. for C24H24N2O4S2
469.1256; found 469.1263. C24H24N2O4S2 (469.13): calcd. C 61.52,
H 5.16, N 5.98, S 13.68; found C 61.26, H 5.15, N 6.01, S 13.56.
1,9-Diamino-3,7-dithiononane·Dihydrochloride (17·2HCl): To
a
solution of 22 (13.2 g, 29.1 mmol) in dry ethanol (50 mL) was
added dropwise a solution of hydrazine (3.1 g, 61.1 mmol) in water
(5 mL). After temporary clearance of the solution a solid precipi-
tate commenced to separate. The whole mixture was heated at re-
flux for 2 h then concentrated hydrochloric acid (12 mL) was added
slowly and the obtained clear solution was stirred for a further
30 min. The alcohol was removed by evaporation and the suspen-
sion was dissolved in water. The solid was filtered off and washed
3
1H NMR (300 MHz, CD2Cl2): δ = 2.87 (s, 6 H, CH3), 3.09 (t, J
3
3
with water. The water was removed by evaporation and the raw = 6.8 Hz, 4 H, CH2), 4.43 (t, J = 6.8 Hz, 4 H, CH2), 7.32 (d, J =
material was crystallized from methanol to obtain 17·2HCl (7.5 g,
8.2 Hz, 4 H, CarH), 7.56 (d, 3J = 8.2 Hz, 4 H, CarH) ppm. 13C
NMR (75 MHz, CD2Cl2): δ = 35.6 (s, CH2), 37.6 (CH3), 70.9 (s,
CH2), 127.5 (t, Car), 129.9 (t, Car), 136.2 (q, Car), 139.7 (q,
96%) as a white solid, m.p. 192 °C. 1H NMR (300 MHz, CD3OD):
3
δ = 1.86–1.96 (m, 2 H, CH2), 2.72 (t, J = 7.1 Hz, 4 H, CH2), 2.86
3
(t, 3J = 6.9 Hz, 4 H, CH2), 3.16 (t, J = 6.7 Hz, 4 H, CH2), 4.84 (s,
C ) ppm. IR (KBr):ν = 3434, 3027, 2942, 1913, 1500, 1428,
˜
ar
6 H, NH3Cl) ppm. 13C NMR (75 MHz, CD3OD): δ = 29.7 (s,
1401 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 258 (4.4) nm. HRMS
(FAB) calcd. for C18H22O6S2 398.0858; found 398.0850.
C18H22O6S2 (398.09): calcd. C 54.25, H 5.56, S 16.09; found C
54.61, H 5.54, S 15.85.
CH ), 30.3 (s, CH ), 31.1 (s, CH ), 40.2 (s, CH ) ppm. IR (KBr): ν
˜
2
2
2
2
= 3440, 3023, 2040, 1718, 1628, 1459, 1412 cm–1. C7H20Cl2N2S2
(267.29): calcd. C 31.46, H 7.54, N 10.48, S 23.99, Cl 26.53; found
C 31.61, H 7.52, Cl 26.42, N 10.34, S 23.71.
4,4Ј-Bis(2-bromoethyl)biphenyl (27):
A solution of 26 (20 g,
1,10-Diamino-3,8-dithiodecane·Dihydrochloride (18·2HCl): To
a
50.2 mmol) in acetone (800 mL) was refluxed with LiBr (26 g,
301.1 mmol) overnight. Water was added to dissolve the precipi-
tated salt and the acetone was removed by evaporation. The aque-
ous layer was extracted 5× with dichloromethane, and the com-
bined organic layers were dried with magnesium sulfate. After evap-
oration of the solvent pure 27 (14.3 g, 81%) was obtained by col-
umn chromatography (alumina; hexane/diethyl ether, 5:1) as a
white solid, m.p. 107 °C. 1H NMR (500 MHz, CD2Cl2): δ = 3.20
solution of 23 (5.5 g, 11.7 mmol) in dry ethanol (25 mL) was added
dropwise a solution of hydrazine (1.23 g, 24.6 mmol) in water
(2 mL). After temporary clearance of the solution a solid precipi-
tate commenced to separate. The whole mixture was heated at re-
flux for 2 h then concentrated hydrochloric acid (12 mL) was added
slowly and the obtained clear solution was stirred for further
30 min. The alcohol was removed by evaporation and the suspen-
sion was dissolved in water. The solid was filtered off and washed
with water. The water was removed by evaporation and the raw
material was crystallized from methanol to obtain 18·2HCl (2.7 g,
83%) as a white solid, m.p. 203 °C. 1H NMR (300 MHz, CD3OD):
3
3
(t, J = 7.5 Hz, 4 H, CH2), 3.63 (t, J = 7.4 Hz, 4 H, CH2), 7.30
3
3
(d, J = 8.1 Hz, 4 H, CarH), 7.56 (d, J = 8.2 Hz, 4 H, CarH) ppm.
13C NMR (125 MHz, CD2Cl2): δ = 33.5 (s, CH2), 39.2 (s, CH2),
127.3 (t, Car), 129.5 (t, Car), 138.4 (q, Car), 139.6 (q, Car) ppm. IR
3
δ = 1.71–1.76 (m, 4 H, CH2), 2.63 (t, J = 7.1 Hz, 4 H, CH2), 2.83
(KBr): ν = 3444, 3052, 3026, 2959, 2930, 2051, 1633, 1493,
˜
3
(t, 3J = 6.9 Hz, 4 H, CH2), 3.15 (t, J = 6.8 Hz, 4 H, CH2), 4.83 (s,
1447 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 260 (4.4) nm. HRMS
(FAB) calcd. for C16H16Br2 367.9599; found 367.9607. C16H16Br2
(367.96): calcd. C 52.21, H 4.38, Br 43.41; found C 52.35, H 4.44,
Br 43.19.
6 H, NH3Cl) ppm. 13C NMR (75 MHz, CD3OD): δ = 29.4 (s,
CH ), 29.7 (s, CH ), 31.9 (s, CH ), 40.0 (s, CH ) ppm. IR (KBr): ν
˜
2
2
2
2
= 3440, 2999, 2045, 2059, 1582, 1508, 1463 cm–1. C8H22Cl2N2S2
(281.31): calcd. C 34.16, H 7.88, N 9.96, S 22.79, Cl 25.21; found
C 34.31, H 7.85, Cl 25.27, N 9.90, S 22.83.
General Procedure for the Condensation of Primary Amines with
Terminal Bromo Compounds to the Tertiary Amines 28–33: A pri-
mary amine (5 mmol) and a terminal bromo-compound (10 mmol)
were added together to a suspension of finely powdered potassium
4,4Ј-Bis(2-hydroxyethyl)biphenyl (25): To a suspension of 4,4Ј-di-
bromobiphenyl (30.00 g, 96 mmol) in dry hexane (1200 mL) was
Eur. J. Inorg. Chem. 2006, 609–620
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617

R. Koschabek, R. Gleiter, F. Rominger
FULL PAPER
3
carbonate (4.9 g, 35 mmol) in acetonitrile (200 mL). The mixture
was stirred intensively and refluxed for 2 d until the starting mate-
rial was consumed. The mixture was filtered and the solvent evapo-
rated. The residue was purified by column chromatography on alu-
mina.
CarH), 7.60 (d, J = 8.5 Hz, 4 H, CarH) ppm. 13C NMR (75 MHz,
CD2Cl2): δ = 33.9 (s, CH2), 34.2 (s, CH2), 56.2 (s, CH2), 56.3 (s,
CH2), 126.2 (t, Car), 127.3 (t, Car), 127.3 (t, Car), 127.5 (t, Car),
128.7 (t, Car), 129.1 (t, Car), 129.2 (t, Car), 129.7 (t, Car), 135.4 (q,
C ), 139.1 (q, C ), 140.6 (q, C ), 141.4 (q, C ) ppm. IR (KBr): ν
˜
ar
ar
ar
ar
= 3440, 3057, 3027, 2943, 2859, 2808, 1486, 1452, 1408 cm–1. UV/
Vis (CH2Cl2): λmax (lg ε) = 258 (4.6) nm. HRMS (FAB) calcd. for
C36H36N 482.2848; found 482.2881. C36H35N (482.28): calcd. C
89.77, H 7.32, N 2.91; found C 89.54, H 7.39, N 3.03.
Tris(2-phenylethyl)amine (28): 945 mg (58%); m.p. 31 °C; cyclohex-
ane/ethyl acetate, 50:1. 1H NMR (300 MHz, CD2Cl2): δ = 2.75–
2.81 (m, 6 H, CH2), 2.84–2.90 (m, 6 H, CH2), 7.21–7.24 (m, 9 H,
3
CarH), 7.32 (t, J = 7.2 Hz, 6 H, CarH) ppm. 13C NMR (75 MHz,
CD2Cl2): δ = 34.2 (s, CH2), 56.4 (s, CH2), 126.2 (t, Car), 128.7 (t,
Tris[2-(biphenyl-4-yl)ethyl]amine (33): 405 mg (15%); m.p. 75 °C;
hexane/diethyl ether, 20:1. 1H NMR: (300 MHz, CD2Cl2): δ =
2.79–2.85 (m, 6 H, CH2), 2.88–2.93 (m, 6 H, CH2), 7.26 (d, 3J =
C ), 129.2 (t, C ), 141.4 (q, C ) ppm. IR (KBr): ν = 3480, 3086,
˜
ar
ar
ar
3028, 2957, 2933, 2864, 2798, 1946, 1873, 1809, 1751, 1600, 1491,
1452 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 258 (3.0) nm. HRMS
(FAB) calcd. for C24H28N 330.2221; found 330.2207. C24H27N
(330.22): calcd. C 87.49, H 8.26, N 4.25; found C 87.44, H 8.22, N
4.40.
3
8.1 Hz, 6 H, CarH), 7.30–7.35 (m, 3 H, CarH), 7.43 (t, J = 7.5 Hz,
3
3
6 H, CarH), 7.52 (d, J = 8.1 Hz, 6 H, CarH), 7.59 (d, J = 7.6 Hz,
6 H, CarH) ppm. 13C NMR (75 MHz, CD2Cl2): δ = 33.8 (s, CH2),
56.2 (s, CH2), 127.3 (t, Car), 127.3 (t, Car), 127.4 (t, Car), 129.1 (t,
Car), 129.7 (t, Car), 139.0 (q, Car), 140.6 (q, Car), 141.4 (q, Car) ppm.
(But-3-ynyl)bis(2-phenylethyl)amine (29): 305 mg (22%) colorless li-
quid; hexane/diethyl ether, 10:1. 1H NMR (300 MHz, CD2Cl2): δ
= 2.01 (m, 1 H, ϵCH), 2.30 (m, 2 H, CH2), 2.72–2.84 (m, 10 H,
CH2), 7.15–7.21 (m, 4 H, CarH), 7.25–7.31 (m, 6 H, CarH) ppm.
13C NMR (75 MHz, CD2Cl2): δ = 17.7 (s, CH2), 34.4 (s, CH2), 53.2
(s, CH2), 56.3 (s, CH2), 69.1 (t, ϵCH), 83.6 (q, ϵC), 126.3 (t, Car),
IR (KBr): ν = 3440, 3027, 2924, 2854, 1486, 1461, 1450 cm–1. UV/
˜
Vis (CH2Cl2): λmax (lg ε) = 258 (4.7) nm. HRMS (FAB) calcd. for
C42H40N 558.3160; found 558.3134. C42H39N (558.32): calcd. C
90.44, H 7.05, N 2.51; found C 90.09, H 7.32, N 2.65.
General Procedure for the Cyclization of α,ω-Diamines with 1,6-Di-
bromo-3-hexyne (16) to the Bicyclic Diynes 4–8: 1,6-Dibromo-3-
hexyne (17) (1.5 g, 6.25 mmol) and the corresponding α,ω-diamines
(2 mmol) were added together to a suspension of finely powdered
potassium carbonate (4.5 g, 33 mmol) in acetonitrile (125 mL). The
mixture was stirred intensively and refluxed for 3 d until the start-
ing material was consumed. The mixture was filtered and the sol-
vent evaporated. The residue was purified by column chromatog-
raphy on alumina.
128.7 (t, C ), 129.2 (t, C ), 141.2 (q, C ) ppm. IR (KBr): ν =
˜
ar
ar
ar
3294, 3026, 2948, 2860, 2812, 2117, 1946, 1868, 1805, 1742, 1602,
1496, 1453 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 260 (2.5) nm.
HRMS (FAB) calcd. for C20H23N 278.1909; found 278.1918.
C20H23N (278.19): calcd. C 86.59, H 8.36, N 5.05; found C 86.64,
H 8.33, N 5.27.
[2-(Biphenyl-4-yl)ethyl]bis(2-phenylethyl)amine (30): 940 mg (47%);
m.p. 54 °C; hexane/diethyl ether, 10:1. 1H NMR (500 MHz,
3
CD2Cl2): δ = 2.74–2.87 (m, 12 H, CH2), 7.18 (d, J = 8.0 Hz, 6 H,
4-Thia-1,7-diazabicyclo[5.6.6]nonadeca-10,16-diyne
(4):
Yield:
3
CarH), 7.26 (m, 6 H, CarH), 7.31–7.34 (m, 1 H, CarH), 7.43 (t, J
227 mg of 4 (41%), column chromatography with cyclohexane/ethyl
3
3
= 7.7 Hz, 2 H, CarH), 7.53 (d, J = 8.0 Hz, 2 H, CarH), 7.60 (d, J
= 7.5 Hz, 2 H, CarH) ppm. 13C NMR (125 MHz, CD2Cl2): δ = 33.7
(s, CH2), 34.1 (s, CH2), 56.1 (s, CH2), 56.2 (s, CH2), 126.1 (t, Car),
127.2 (t, Car), 127.2 (t, Car), 127.3 (t, Car), 128.5 (t, Car), 129.0 (t,
Car), 129.1 (t, Car), 129.6 (t, Car), 139.0 (q, Car), 140.5 (q, Car),
1
acetate, 20:1, m.p. 69 °C. H NMR (500 MHz, CD2Cl2): δ = 2.24–
3
2.35 (m, 8 H, CH2), 2.52–2.56 (m, 8 H, CH2), 2.76 (t, J = 6.0 Hz,
4 H, CH2), 2.98 (t, 3J = 6.0 Hz, 4 H, CH2) ppm. 13C NMR
(125 MHz, CD2Cl2): δ = 19.5 (s, CH2), 30.6 (s, CH2), 53.4 (s, CH2),
56.5 (s, CH2), 80.6 (q, Calkyne) ppm. IR (KBr): ν = 3447, 2900,
˜
141.3 (q, C ) ppm. IR (KBr): ν = 3025, 2946, 1597, 1495, 1486,
˜
ar
2835, 2801, 2781, 2731, 1449, 1432 cm–1. Raman: ν = 2228,
˜
1453 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 256 (4.4) nm. HRMS
(EI+) calcd. for C30H31N 405.2457; found 405.2448. C30H31N
(405.24): calcd. C 88.84, H 7.70, N 3.45; found C 88.44, H 7.84, N
3.57.
2291 cm–1. HRMS (FAB) calcd. for C16H25N2S 277.1738; found
277.1731. C16H24N2S (272.17): calcd. C 69.52, H 8.75, N 10.13, S
11.60; found C 69.31, H 8.77, N 10.04, S 11.43.
4-Selena-1,7-diazabicyclo[5.6.6]nonadeca-10,16-diyne (5): Yield:
212 mg of 5 (33%), column chromatography with cyclohexane/ethyl
acetate, 20:1, m.p. 107 °C. 1H NMR (300 MHz, CD2Cl2): δ = 2.26–
2.33 (m, 8 H, CH2), 2.52–2.56 (m, 8 H, CH2), 2.89 (t, 3J = 6.1 Hz, 4
H, CH2), 3.01 (t, 3J = 6.1 Hz, 4 H, CH2) ppm. 13C NMR (75 MHz,
CD2Cl2): δ = 19.5 (s, CH2), 22.2 (s, CH2), 53.3 (s, CH2), 57.4 (s,
Bis[2-(biphenyl-4-yl)ethyl]but-3-ynylamine (31): 553 mg (25%) col-
orless oil; hexane/diethyl ether, 10:1. 1H NMR: (500 MHz,
4
3
CD2Cl2): δ = 2.04 (t, J = 2.6 Hz, 1 H, ϵCH), 2.37 (dt, J = 4.8,
4J = 2.6 Hz, 2 H, CϵCCH2), 2.82–2.87 (m, 10 H, CH2), 7.29 (d,
3J = 8.1 Hz, 4 H, CarH), 7.34 (pt, 3J = 7.4 Hz, 2 H, CarH), 7.44
(pt, 3J = 7.7 Hz, 4 H, CarH), 7.54 (d, 3J = 8.1 Hz, 4 H, CarH), 7.61
(d, 3J = 7.2 Hz, 4 H) ppm. 13C NMR: (125 MHz, CD2Cl2): δ =
17.6 (s, CH2), 33.9 (s, CH2), 53.10 (s, CH2), 56.1 (s, CH2), 69.10 (t,
ϵCH), 83.6 (q, ϵC), 127.2 (t, Car), 127.3 (t, Car), 127.4 (t, Car),
129.1 (t, Car), 129.6 (t, Car), 139.1 (q, Car), 140.3 (q, Car), 141.3
CH2), 80.6 (q, Calkyne) ppm. IR: (KBr): ν = 3445, 2951, 2903, 2790,
˜
2728, 1453, 1428 cm–1. Raman: ν = 22278, 22891 cm–1. HRMS
˜
(FAB) calcd. for C16H25N282Se 327.1184; found 327.1144.
C16H24N2Se (327.12): calcd. C 59.43, H 7.48, N 8.66; found C
59.28, H 7.55, N 8.58.
(q, C ) ppm. IR (KBr): ν = 3441, 3307, 3055, 3026, 1487, 1449,
˜
ar
1407 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 258 (4.6) nm. HRMS
(FAB) calcd. for C32H31N 430.2534; found 430.2534. C32H31N
(430.25): calcd. C 89.47, H 7.27, N 3.26; found C 89.08, H 7.25, N
3.32.
4,7-Dithia-1,10-diazabicyclo[8.6.6]docosa-13,19-diyne (6): Yield:
291 mg of 6 (43%), column chromatography with cyclohexane/ethyl
1
acetate, 50:1, m.p. 134 °C. H NMR (300 MHz, CD2Cl2): δ = 2.26
(mt, 8 H, CH2), 2.44–2.48 (m, 8 H, CH2), 2.61–2.65 (m, 8 H, CH2),
2.74 (s, 4 H, SCH2CH2S) ppm. 13C NMR (75 MHz, CDCl3): δ =
18.7 (s, CH2), 30.4 (s, CH2), 31.8 (s, CH2), 53.2 (s, CH2), 54.3 (s,
Bis[2-(biphenyl-4-yl)ethyl](2-phenylethyl)amine (32): 566 mg (56%);
m.p. 82 °C; hexane/diethyl ether, 10:1. 1H NMR (300 MHz,
3
CD2Cl2): δ = 2.78–2.92 (m, 12 H, CH2), 7.20 (d, J = 7.6 Hz, 3 H, CH2), 79. 5 (q, Calkyne) ppm. IR (KBr): ν = 3440, 2956, 2900, 2801,
˜
CarH), 7.26 (d, 3J = 8.2 Hz, 6 H, CarH), 7.31–7.36 (m, 2 H, 2730, 1630, 1455, 1421 cm–1. Raman: ν = 22368, 2300 cm–1. HRMS
˜
3
3
CarH),7.44 (t, J = 8.0 Hz, 4 H, CarH), 7.53 (d, J = 8.2 Hz, 4 H,
(FAB) calcd. for C18H29N2S2 337.1772; found 337.1735.
618
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 609–620

Synthesis and Properties of Cryptands with a Thioether Bridge and π-Donors
FULL PAPER
C18H28N2S2 (337.18): calcd. C 64.24, H 8.39, N 8.32, S 19.05;
found C 64.25, H 8.33, N 8.26, S 19.21.
(FAB) calcd. for C40H49N2S2 621.3337; found 621.3317.
C40H48N2S2 (621.33): calcd. C 77.37, H 7.79, N 4.51, S 10.33;
found C 77.01, H 7.75, N 4.60, S 10.43.
4,8-Dithia-1,11-diazabicyclo[9.6.6]tricosa-14,20-diyne (7): Yield
360 mg of 7 (53%), column chromatography with cyclohexane/ethyl
General Procedure for the Synthesis of Copper(I) Complexes
1
[4·Cu+][CF3SO3] and [5·Cu+][CF3SO3]: To a solution of the cop-
per(i) triflate toluene complex (61 mg, 0.2 mmol) in anhydrous
dichloromethane (5 mL) was added in the absence of light a solu-
tion of the corresponding cryptand (0.1 mmol) in anhydrous
dichloromethane (5 mL). After stirring for 1 h the mixture was fil-
tered and evaporation of the solvent gave the corresponding cop-
per(i) complex in quantitative yield.
acetate, 50:1, m.p. 89 °C. H NMR (300 MHz, CDCl3): δ = 1.91–
3
2.00 (q, J = 7.1 Hz, 2 H, CH2), 2.29 (br. s, 8 H, CH2), 2.57 (br. s,
3
12 H, CH2), 2.71 (t, J = 7.0 Hz, 8 H, SCH2CH2CH2S) ppm. 13C
NMR (75 MHz, CDCl3): δ = 19.3 (s, CH2), 28.2 (s, CH2), 29.2 (s,
CH2), 30.0 (s, CH2), 53.7 (s, CH2), 54.5 (s, CH2), 79.9 (q,
Calkyne) ppm. IR (KBr): ν = 3446, 2943, 2924, 2901, 2821, 2745,
˜
2725, 1458, 1434, 1424 cm–1. Raman: ν = 2231, 2293 cm–1. HRMS
˜
(FAB) calcd. for C19H31N2S2 351.1928; found 351.1920.
C19H30N2S2 (351.19): calcd. C 65.09, H 8.62, N 7.99, S 18.29;
found C 64.71, H 8.52, N 7.94, S 18.38.
Complex [4·Cu+][CF3SO3 ]: 1H NMR (500 MHz, CD2Cl2): δ = 2.71
–
(t, 3J = 5.6 Hz, 8 H, CH2), 2.69–2.72 (m, 4 H, CH2), 2.75–2.77 (m,
4 H, CH2), 2.84–2.88 (m, 4 H, CH2), 2.95 (s, 4 H, CH2) ppm. 13C
NMR (125 MHz, CD2Cl2): δ = 19.8 (s, CH2), 30.9 (s, CH2), 37.8
(s, CH2), 54.2 (s, CH2), 55. 5 (q, OTf–), 80.2 (q, Calkyne) ppm. IR
4,9-Dithia-1,12-diazabicyclo[10.6.6]tetracosa-15,21-diyne (8): Yield:
275 mg of 8 (39%), column chromatography with cyclohexane/ethyl
1
(KBr): ν = 3444, 2924, 2906, 2839, 1634, 1457, 1426 cm–1. Raman:
acetate, 50:1, m.p. 72 °C. H NMR (300 MHz, CDCl3): δ = 1.79–
˜
ν = 2231 cm–1. HRMS (FAB) calcd. for C H CuN S 341.0939;
1.83 (m, 4 H, CH2), 2.32 (s, 8 H, CH2), 2.62–2.70 (m, 20 H,
CH2) ppm. 13C NMR (75 MHz, CDCl3): δ = 19.3 (s, CH2), 28.7 (s,
CH2), 31.0 (s, CH2), 31.8 (s, CH2), 53.89 (s, CH2), 55.4 (s, CH2),
˜
16 24
2
found 341.0938.
Complex [5·Cu+][CF3SO3 ]: 1H NMR (500 MHz, CD2Cl2): δ = 2.64
(t, 3J = 6.0 Hz, 8 H, CH2), 2.71–2.78 (m, 8 H, CH2), 2.86–2.91 (m,
–
80.2 (q, Calkyne) ppm. IR (KBr): ν = 3440, 2939, 2900, 2819, 2744,
˜
1628, 1456, 1422, 1422 cm–1. Raman: ν = 2237, 2297 cm–1. HRMS
˜
3
3J = 6.0 Hz, 4 H, CH2), 2.98 (t, J = 5.3 Hz, 4 H, CH2), 2.95 (s, 4
(FAB) calcd. for C20H32N2S2 365.2095; found 365.2056.
C20H32N2S2 (365.21): calcd. C 65.88, H 8.85, N 7.68, S 17.59;
found C 65.70, H 8.84, N 7.65, S 17.30.
H, CH2) ppm. 13C NMR (125 MHz, CD2Cl2): δ = 18.9 (s, CH2),
30.9 (s, CH2), 53.9 (s, CH2), 56.4 (s, CH2), 80.0 (q, Calkyne) ppm.
IR (KBr): ν = 3441, 2922, 2868, 1630, 1460, 1427 cm–1. HRMS
˜
General Procedure for the Cyclization of α,ω-Diamines with 4,4Ј-
Bis(2-bromoethyl)biphenyl (27): To the bicyclic compounds 9 and
10 4,4Ј-bis(2-dibromoethyl)biphenyl (27) (6.7 g, 10 mmol) and the
diamines 17 and 18 (4 mmol), respectively, were added together to
a suspension of finely powdered potassium carbonate (8.5 g,
61 mmol) in acetonitrile (400 mL). The mixture was stirred inten-
sively and refluxed for 5 d until the starting material was consumed.
The mixture was filtered and the solvent evaporated. The residue
was purified by column chromatography on alumina.
(FAB) calcd. for C16H24CuN2Se 387.0400; found 387.0406.
General Procedure for the Synthesis of Silver Complexes
[6·Ag+][CF3SO3 ], [10·2(Ag+)][CF3SO3 ]2, [28·Ag+][CF3SO3 ], and
–
–
–
–
[33·Ag+][CF3SO3 ]: To
a solution of silver triflate (53 mg,
0.2 mmol) in anhydrous dichloromethane (5 mL) was added in the
absence of light solution of the corresponding cryptand
a
(0.1 mmol) in anhydrous dichloromethane (5 mL). After stirring for
1 h the mixture was filtered and evaporation of the solvent gave the
corresponding silver complex in quantitative yield.
4,8-Dithia-14,15,20,21-tetrabenzena-1,11-diazabicyclo[9.6.6]tricosa-
phane (9): 476 mg (20%); hexane/diethyl ether, 20:1, m.p. 180 °C
(decomp.). 1H NMR (500 MHz, CD2Cl2): δ = 0.49–0.54 (q, 3J =
–
Complex [6·Ag+][CF3SO3 ]: 1H NMR (300 MHz, CD2Cl2): δ =
2.46–2.61 (m, 16 H, CH2), 2.69–2.73 (m, 4 H, CH2), 2.77–2.81 (m,
4 H, CH2), 2.93 (s, 4 H, SCH2CH2S) ppm. 13C NMR (75 MHz,
CD2Cl2): δ = 18.6 (s, CH2), 29.3 (s, CH2), 30.7 (s, CH2), 53.0 (s,
3
7.4 Hz, 2 H, SCH2CH2), 1.13 (t, J = 7.1 Hz, 4 H, CH2), 1.30 (t,
3J = 7.4 Hz, 4 H, SCH2CH2CH2S), 2.21 (t, 3J = 7.1 Hz, 4 H, CH2),
2.51–2.55 (m, 4 H, CH2), 2.72–2.77 (m, 4 H, CH2), 2.89–2.94 (m,
4 H, CH2), 2.97–3.02 (m, 4 H, CH2), 7.22 (d, 3J = 8.1 Hz, 8 H,
CarH), 7.45 (d, 3J = 8.1 Hz, 8 H, CarH) ppm. 13C NMR (125 MHz,
CD2Cl2): δ = 30.6 (s, CH2), 30.8 (s, CH2), 31.9 (s, CH2), 33.6 (s,
CH2), 53.7 (s, CH2), 53.9 (s, CH2), 126.3 (t, Car), 130.5 (t, Car),
CH2), 53.1 (s, CH2), 79.3 (q, Calkyne) ppm. IR (KBr): ν = 3444,
˜
2963, 2920, 2849, 1461, 1434 cm–1. HRMS (FAB) calcd. For
C18H28AgN2S2 445.0741; found 445.0701.
Complex [7·Ag+][CF3SO3 ]: 1H NMR (300 MHz, CD2Cl2): δ = 1.79
–
(t, 3J = 6.6 Hz, 4 H, CH2), 2.13–2.22 (m, 2 H, CH2), 2.47–2.54 (m,
138.3 (q, C ), 139.5 (t, C ) ppm. IR (KBr): ν = 3439, 2910, 2849,
˜
3
ar
ar
8 H, CH2), 2.61 (m, 4 H, CH2), 2.74 (t, J = 5.5 Hz, 4 H, CH2),
2788, 1733, 1499, 1457, 1422 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) =
260 (4.8) nm. HRMS (FAB) calcd. for C39H47N2S2 607.3181; found
607.3166. C39H46N2S2 (607.32): calcd. C 77.18, H 7.64, N 4.62, S
10.57; found C 77.04, H 7.65, N 4.65, S 10.77.
2.86–2.93 (m, 8 H, CH2), 2.63–3.68 (m, 4 H, CH2) ppm. 13C NMR
(75 MHz, CD2Cl2): δ = 19.4 (s, CH2), 25.9 (s, CH2), 31.6 (s, CH2),
32.3 (s, CH2), 53.3 (s, CH2), 53.7 (s, CH2), 68.0 (q, OTf–), 79.7 (q,
Calkyne) ppm. IR (KBr): ν = 3441, 2963, 2916, 2840, 2823, 1629,
˜
1459, 1446, 1433, 1418 cm–1. Raman: ν = 2206, 2281 cm–1. HRMS
4,9-Dithia-15,16,21,22-tetrabenzena-1,12-diazabicyclo[10.6.6]tetra-
cosaphane (10): Yield: 384 mg of 10 (16%), column chromatog-
raphy with hexane/diethyl ether, 10:1, m.p. 189 °C (decomp.). 1H
NMR (500 MHz, CD2Cl2): δ = 0.67 (m, 4 H, SCH2CH2), 1.53–
˜
(FAB) calcd. for C19H30AgN2S2 459.0898; found 459.0888.
Complex [8·Ag+][CF3SO3 ]: 1H NMR (500 MHz, CD2Cl2): δ = 1.92
–
(s, 4 H, CH2), 2.53–2.66 (m, 16 H, CH2), 2.76 (t, 3J = 6.5 Hz, 4 H,
3
3
1.54 (pd, J = 8.9 Hz, 4 H, CH2), 1.70 (t, J = 6.6 Hz, 4 H, CH2),
2.36 (t, 3J = 6.6 Hz, 4 H, CH2), 2.54–2.59 (m, 4 H, CH2), 2.73–
2.78 (m, 4 H, CH2), 2.87–2.94 (m, 8 H, CH2), 7.16 (d, 3J = 8.0 Hz,
8 H, CarH), 7.32 (d, 3J = 8.0 Hz, 8 H, CarH) ppm. 13C NMR
(125 MHz, CD2Cl2): δ = 30.0 (s, CH2), 31.0 (s, CH2), 31.1 (s, CH2),
33.1 (s, CH2), 54.2 (s, CH2), 55.2 (s, CH2), 126.5 (t, Car), 130.2 (t,
3
CH2), 2.91 (s, 4 H, CH2), 2.98 (t, J = 6.5 Hz, 4 H, CH2) ppm. 13C
NMR (125 MHz, CD2Cl2): δ = 18.5 (s, CH2), 26.4 (s, CH2), 31.4
(s, CH2), 32.2 (s, CH2), 53.4 (s, CH2), 60.9 (q, OTf–), 78.9 (q,
Calkyne) ppm. IR (KBr):ν
= 3443, 2924, 2846, 1629, 1457,
˜
1439 cm–1. HRMS (FAB) calcd. for C20H32AgN2S2 471.1058;
found 471.1075.
C ), 138.6 (q, C ), 139.3 (q, C ) ppm. IR (KBr): ν = 3440, 3022,
˜
ar
ar
ar
–
2963, 2908, 2855, 2783, 2729, 1738, 1632, 1500, 1456, 1448,
Complex [9·Ag+][CF3SO3 ]: 1H NMR (500 MHz, CD2Cl2): δ = 0.77
1402 cm–1. UV/Vis (CH2Cl2): λmax (lg ε) = 258 (4.5) nm. HRMS (s, 2 H, CH2), 1.63 (s, 4 H, CH2), 2.27 (t, J = 6.8 Hz, 4 H, CH2),
3
Eur. J. Inorg. Chem. 2006, 609–620
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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619

R. Koschabek, R. Gleiter, F. Rominger
FULL PAPER
[5] a) J. Buter, R. M. Kellogg, J. Chem. Soc., Chem. Commun.
1980, 466–467; b) J. Buter, R. M. Kellogg, J. Org. Chem. 1981,
46, 4481–4485.
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1055–1056; c) R. A. Pascal, Jr., J. Spergel, D. Van Engen, Tet-
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2096; Angew. Chem. Int. Ed. 1999, 38, 1968–1971.
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172.
2.62–2.67 (m, 4 H, CH2), 2.84–2.89 (m, 4 H, CH2), 3.00–3.05 (m,
4 H, CH2), 3.11–3.17 (m, 4 H, CH2), 7.39 (d, 3J = 7.6 Hz, 8 H,
3
C H), 7.55 (d, J = 7.6 Hz, 8 H, C H) ppm. IR: (KBr): ν = 3449,
˜
ar
ar
3022, 2941, 2915, 2795, 2736, 1626, 1499, 1450, 1425, 1407 cm–1.
UV/Vis (CH2Cl2): λmax (lg ε) = 270 (3.4) nm. HRMS (FAB) calcd.
for C39H46AgN2S2 715.2150; found 715.2158.
Complex [10·2(Ag+)][CF3SO3 ]2: 1H NMR (300 MHz, CD2Cl2): δ
–
= 1.01 (s, 4 H, CH2), 2.44 (s, 4 H, CH2), 2.51 (br. s, 4 H, CH2),
2.75 (br. s, 4 H, CH2), 2.80–2.88 (m, 4 H, CH2), 2.95–3.05 (m, 4
H, CH2), 3.09–3.21 (m, 8 H, CH2), 7.56 (d, 3J = 7.8 Hz, 8 H, CarH),
7.68 (d, 3J = 7.1 Hz, 8 H, CarH) ppm. 13C NMR (75 MHz,
CD2Cl2): δ = 27.4 (s, CH2), 31.8 (s, CH2), 33.3 (s, CH2), 34.6 (s,
CH2), 49.6 (s, CH2), 53.7 (s, CH2), 54.1 (s, CH2), 54.4 (s, CH2),
67.9 (q, OTf–), 124.7 (t, Car), 125.8 (t, Car), 127.3 (t, Car), 138.0 (q,
C ), 139.0 (q, C ) ppm. IR (KBr): ν = 3444, 2926, 2792, 1627,
˜
[9] A. Kunze, S. Bethke, R. Gleiter, F. Rominger, Org. Lett. 2000,
ar
ar
1500, 1451 cm–1. HRMS (FAB) calcd. for C40H47Ag2N2S2
835.1279; found 835.1303. C42H48Ag2F6N2O6S4 (863.88): calcd. C
44.54, H 4.26, N 2.47; found C 44.84, H 4.60, N 2.57.
2, 609–612.
[10] V. Wolfart, R. Gleiter, H. Irngartinger, T. Oeser, C. Krieger,
Eur. J. Org. Chem. 1998, 2803–2809.
[11]
G. G. Hermann, A. M. Goeminne, Z. Eeckhaut, J. Coord.
Chem. 1979, 9, 1–5.
Complex [28·Ag+][CF3SO3 ]: Colorless crystals, soluble in dichloro-
–
methane or chloroform, m.p. 145 °C (decomp.). 1H NMR
[12]
V. Srivastava, R. Batheja, A. K. Singh, J. Organomet. Chem.
1994, 484, 93–96.
3
(500 MHz, CD2Cl2): δ = 2.70 (t, J = 6.0 Hz, 6 H, CH2), 2.94 (t,
3J = 6.0 Hz, 6 H, CH2), 6.84 (d, 3J = 7.0 Hz, 6 H, CarH), 7.30–
7.37 (m, 9 H, CarH) ppm. 13C NMR (125 MHz, CD2Cl2): δ = 33.0
(s, CH2), 57.6 (s, CH2), 124.2 (t, Car), 127.7 (t, Car), 130.6 (t, Car),
[13]
[14]
H. R. Ing, R. H. F. Manske, J. Chem. Soc. 1926, 2348–2351.
M. Brudermüller, H. Musso, A. Wagner, Chem. Ber. 1988, 121,
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[15]
[16]
[17]
[18]
M. K. W. Choi, H. S. He, P. H. Toy, J. Org. Chem. 2003, 68,
139.2 (q, C ) ppm. IR (KBr): ν = 3441, 3085, 3061, 3026, 2951,
˜
ar
2861, 2799, 1627, 1603, 1495, 1453 cm–1. HRMS (FAB) calcd. for
C24H27109AgN 438.1191; found 438.1229. C25H27AgF3NO3S
(586.42)·0.75 CH2Cl2: calcd. C 47.57, H 4.42, N 2.15, S 4.93; found
C 47.50, H 4.42, N 2.31, S 5.10.
9831–9834.
M. Kawasaki, M. Goto, S. Kawabata, T. Kometani, Tetrahe-
dron: Asymmetry 2001, 12, 585–596.
J. W. Dankwardt, Angew. Chem. 2004, 116, 2482–2486; Angew.
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D. Pérez, G. Burés, E. Guitián, L. Castedo, J. Org. Chem. 1996,
61, 1650–1654.
–
Complex [33·Ag+][CF3SO3 ]: Colorless, light-sensitive crystals, sol-
uble in dichloromethane or chloroform, m.p. 173 °C (decomp.). 1H
NMR (500 MHz, CD2Cl2): δ = 2.83 (t, 3J = 5.8 Hz, 6 H, CH2),
[19] C. Qioa, H.-B. Jeon, L. M. Sayre, J. Am. Chem. Soc. 2004, 126,
3
3
8038–8045.
2.99 (t, J = 5.8 Hz, 6 H, CH2), 6.96 (d, J = 7.9 Hz, 6 H, CarH),
7.43 (d, 3J = 8.0 Hz, 6 H, CarH) ppm. 13C NMR (125 MHz,
CD2Cl2): δ = 32.4 (s, CH2), 57.1 (s, CH2), 124.6 (t, Car), 126.9 (t,
Car), 127.9 (t, Car), 128.7 (t, Car), 129.6 (t, Car), 138.1 (q, Car), 138.6
[20] J. L. Pierre, P. Baret, P. Chautemps, M. Armand, J. Am. Chem.
Soc. 1981, 103, 2986–2988.
[21] T. Lahtinen, E. Wegelius, K. Airola, E. Kolehmainen, K. Ris-
sanen, J. Prakt. Chem. 1999, 341, 237–244.
(q, C ), 140.2 (q, C ) ppm. IR (KBr): ν = 3441, 3028, 2929, 1625,
˜
ar
ar
[22] T. Lahtinen, E. Wegelius, K. Rissanen, New J. Chem. 2001, 25,
1519, 1487, 1458, 1407 cm–1. HRMS (FAB) calcd. for
C43H39109AgN 666.2130; found 666.2112. C43H29AgF3NO3S
(804.64): calcd. C 63.39, H 4.82, N 1.71, S 3.94; found C 63.28, H
4.89, N 2.04, S 4.28.
905–911.
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2784; P. G. Jones, P. Bubentschik, S. Heirtzler, Acta Crys-
tallogr., Sect. C 1996, 52, 1380–1384; P. G. Jones, F. R.
Heirtzler, H. Hopf, Acta Crystallogr., Sect. C 1996, 52, 1384–
1388.
Acknowledgments
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We are grateful to the Deutsche Forschungsgemeinschaft and the
Fonds der Chemischen Industrie for financial support. We thank
Mrs. P. Krämer for typing and graphical work.
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Received: July 29, 2005
Published Online: December 13, 2005
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Eur. J. Inorg. Chem. 2006, 609–620