Organotin-substituted crown ethers for ditopic complexation of anions and cations

Article abstract of DOI:10.1002/ejic.200500191

The syntheses of the organotin-substituted crown ethers m-(Ph ₂XSnCH₂CH₂)-15-benzocrown-5 (2, X = Ph; 3, X = I; 4, X = Cl; 5, X = NCS) and the salt [m-(Ph₃SnCH₂CH ₂)-15-benzocrown-5·Na]⁺SCN^- (2a) are reported. Compounds 2a and 4 (as its aqua complex 4·H₂O) are characterized by single-crystal X-ray diffraction sudies. Multinuclear NMR spectroscopy and electrospray mass spectrometry reveal the triorganotin chloride 4 to be a ditopic host towards sodium rhodanide. This statement is further supported by the ability of compound 4 to transport sodium rhodanide through an organic membrane. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Full text of DOI:10.1002/ejic.200500191

FULL PAPER
Organotin-Substituted Crown Ethers for Ditopic Complexation of Anions and
Cations[‡]
Gregor Reeske,[a] Markus Schürmann,[a] Burkhard Costisella,[a] and Klaus Jurkschat*[a]
Dedicated to Prof. W.-W. Du Mont on the occasion of his 60th birthday
Keywords: Ditopic complexation / Host-guest chemistry / NMR spectroscopy / X-ray crystallography / Tin
The syntheses of the organotin-substituted crown ethers m-
(Ph2XSnCH2CH2)-15-benzocrown-5 (2, X = Ph; 3, X = I; 4, X
chloride 4 to be a ditopic host towards sodium rhodanide.
This statement is further supported by the ability of com-
= Cl; 5, X = NCS) and the salt [m-(Ph3SnCH2CH2)-15-benzo- pound 4 to transport sodium rhodanide through an organic
crown-5·Na]+SCN– (2a) are reported. Compounds 2a and 4
(as its aqua complex 4·H2O) are characterized by single-crys-
membrane.
tal X-ray diffraction sudies. Multinuclear NMR spectroscopy (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
and electrospray mass spectrometry reveal the triorganotin
Germany, 2005)
ethers and demonstrate that such compounds are able to
complex and transport sodium rhodanide in nonpolar or-
ganic solvents.
Introduction
The simultaneous recognition and sensing of anions and
cations is a new area of increasing research activities.[1,2]
Practical applications of ion-pair recognition range from
complexation of zwitterionic amino acids and peptides,[3,4]
the transport of ion pairs across biological membranes[5–12]
to solubility enhancement of ion pairs in nonpolar solvents
for ion extraction.[13] Ion-pair receptors known so far are
based on the combination of crown compounds or calixar-
enes with (i) ammonium groups exploiting hydrogen bond-
ing[14,15] or (ii) Lewis acidic groups.[16–20] Straightforward
examples of the latter case involve the work of Reetz et
al.[18a] on an organoboron-substituted crown ether, and
Willem et al.[18b] who reported the sodium rhodanide com-
plex of triorganotin carboxylates containing the [18]crown-
6 and [15]crown-5 substituents. However, an essential short-
coming of the latter compounds is the kinetic lability of
the tin–carboxylate bond, which makes the corresponding
zwitterionic complexes unstable in solution.[18b]
Results and Discussion
Synthetic Aspects and Molecular Structures in the Solid
State
The reaction of 4-vinylbenzo-15-crown-5[24,25] (1) with
triphenyltin hydride provided [2-(6,7,9,10,12,13,15,16-octa-
hydro-5,8,11,14,17-pentaoxabenzocyclopentadec-2-yl)ethyl]-
triphenylstannane (2) as a colorless oil (Scheme 1).
Treatment of the tetraorganostannane 2 with 1 mol-
equiv. of iodine gave the triorganotin iodide 3. The latter
was quantitatively converted into its chloride derivative 4
by reaction with AgCl in acetonitrile over a period of 14 d.
The reaction of triorganotin iodide 3 with AgSCN in
CH3CN gave the triorganotin rhodanide 5 in quantitative
yield.
The treatment of 2 with NaSCN in ethanol provided the
corresponding sodium rhodanide complex 2a as a colorless
solid. Single crystals of 2a suitable for X-ray diffraction
analyses were obtained by recrystallization from dichloro-
methane/n-hexane.
In continuation of our own studies on organotin halides
as Lewis acids for selective complexation of anions[21–23] we
report here the synthesis and structures of kinetically more
stable carbon-bonded organotin-functionalized crown
[‡] This work contains part of the PhD Thesis of G. R., Dortmund
University, 2004. Parts of this work were first presented at the
XI. International Conference on the Coordination and Organo-
metallic Chemistry of Germanium, Tin, and Lead, Santa Fe,
NM, USA, June 27–July 2, 2004, Book of Abstracts, p26.
[a] Lehrstuhl für Anorganische Chemie II der Universität Dort-
mund,
The molecular structure of 2a is shown in Figure 1 and
selected geometric parameters are collected in Table 1.
The sodium cation is coordinated by five oxygen atoms
with Na–O distances ranging between 2.317(7) and
2.469(6) Å. These values are in line with those reported for
similar compounds.[18] The rhodanide anion is located close
44221 Dortmund, Germany
Fax: +49-231-7555048
E-mail: klaus.jurkschat@uni-dortmund.de
Eur. J. Inorg. Chem. 2005, 2881–2887
DOI: 10.1002/ejic.200500191
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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G. Reeske, M. Schürmann, B. Costisella, K. Jurkschat
FULL PAPER
Scheme 1. Synthesis of the organotin-substituted crown ethers. i) Ph3SnH, AIBN; ii) NaSCN, EtOH; iii) I2, CH2Cl2, – PhI; iv) AgCl,
CH3CN, – AgI; v) AgSCN, CH3CN, – AgI.
Figure 1. Molecular structure of the sodium rhodanide complex
2a. Atomic displacement parameters are drawn at 30% probability
level.
Figure 2. Molecular structure of 4·H2O. Atomic displacement
parameters are drawn at 30% probability level.
Table 1. Selected bond lengths [Å] and angles [°] for 2a.
Table 2. Selected bond lengths [Å] and angles [°] for 4·H2O.
Sn–C(11)
Sn–C(21)
Sn–C(31)
S–C(51)
2.141(9) Na–N
2.125(9) Na–O(1)
2.141(7) Na–O(2)
1.625(11) Na–O(3)
1.164(10) Na–O(4)
Na–O(5)
2.344(9)
2.453(5)
2.438(6)
2.313(7)
2.469(6)
2.375(6)
117.0(2)
141.0(3)
71.5(2)
Sn–C(1)
Sn–C(11)
Sn–C(21)
Sn–Cl(1)
2.125(4) O(1)–C(26)
2.109(4) O(2)–C(27)
2.125(4) O(5)–C(33)
2.453(1)
2.469(4)
1.359(5)
1.430(5)
1.406(5)
1.430(5)
N–C(51)
Sn–O(6W)
O(1)–C(25)
C(1)–Sn–Cl(1)
C(1)–Sn–O(6W)
Cl(1)–Sn–O(6W) 176.0(11) C(21)–Sn–C(1)
C(11)–Sn–C(1) 116.0(16) C(21)–Sn–Cl(1)
C(1)–Sn–C(11)
C(1)–Sn–C(21)
C(1)–Sn–C(31)
C(21)–Sn–C(11)
C(21)–Sn–C(31)
C(31)–Sn–C(11)
O(1)–Na–O(4)
O(1)–Na–O(2)
108.0(4)
O(1)–Na-(O3)
O(2)–Na–O(4)
O(3)–Na-(O2)
O(3)–Na-(O4)
O(3)–Na-(O5)
O(5)–Na-(O1)
O(5)–Na-(O2)
O(5)–Na-(O4)
95.0(12) C(11)–Sn–Cl(1)
81.0(16) C(11)–Sn–O(6W) 86.5(14)
96.5(11)
110.5(4)
108.0(4)
105.5(4)
112.0(4)
111.0(3)
125.5(2)
66.5(2)
121.5(17)
96.0(13)
70.5(3)
120.0(3)
62.75(20)
127.5(2)
67.5(2)
C(11)–Sn–C(21) 118.5(17) C(21)–Sn–O(6W) 83.5(16)
The compound crystallizes monoclinically with one
molecule in the unit cell. The tin atom in 4·H2O is pentaco-
ordinate and adopts a distorted trigonal-bipyramidal con-
to the sodium cation with an Na–N distance of 2.344(9) Å. figuration [geometrical goodness Δ(Σϑ) = 68.5°].[26,27] The
The tin atom shows the expected tetrahedral configuration. equatorial positions are occupied by C(1), C(11), C(21) and
Crystallization of the triorganotin chloride 4 at –5 °C the axial positions by Cl(1) and the water oxygen atom. The
from CH2Cl2/Et2O (1:2) in the presence of air moisture af- tin atom is displaced by 0.22 Å from the plane defined by
forded single crystals of the aqua complex 4·H2O as its C(1), C(11), C(21) in the direction of Cl(1). The Sn(1)–Cl(1)
CH2Cl2 solvate.
The molecular structure of 4·H2O is shown in Figure 2, tively, are comparable with those of other aqua complexes
selected geometric parameters are collected in Table 2.
of organotin chlorides.[28,29] In CH2Cl2 solution, compound
and Sn–O(6W) distances of 2.453(1) and 2.469(4) Å, respec-
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Organotin-Substituted Crown Ethers for Ditopic Complexation
FULL PAPER
4·H2O shows a dissociation equilibrium between 4·H2O and 1 mol-equiv. of NaSCN had been added showed in com-
4 + H2O. The equilibrium is fast on the NMR time-scale parison to compound 4 a low-frequency-shifted single
with the population of 4 + H2O dominating at room tem- broad resonance at δ = –225 ppm (ν1/2 = 2013 Hz) which
perature (δ119Sn = 2 ppm). However, at –70 °C the aqua at –60 °C shifted to δ = –248 ppm (ν1/2 = 937 Hz). The 13C
complex 4·H2O dominates (δ119Sn = –155 ppm). These re- NMR spectrum of the same solution showed 1J(13C-117/
sults are supported by NOE decoupling experiments at dif- 119Sn) coupling constants of 595/621 and 716/751 Hz to the
ferent temperatures. At room temperature the water proton Sn–CH2 and Sn–Ci carbon atoms, respectively, that are
resonance shows a large NOE to the resonances of the larger than the corresponding couplings of 426/446 and
crown ether ring suggesting hydrogen bonding to the oxy- 540/566 Hz measured for compound 4. Both the 119Sn
1
gen atoms of the latter. Upon lowering of the temperature, chemical shifts and the J(13C-117/119Sn) coupling constants
this NOE becomes smaller, which implies a larger distance clearly indicate the tin atom in the complex [4·NaSCN] to
between the crown ether protons and the water protons.
be pentacoordinate. The ultimate evidence for the coordina-
tion of the rhodanide anion to the tin atom stems (i) from
the observation of a J(13C-117/119Sn) coupling of 59 Hz to
the rhodanide carbon atom and (ii) from an HMBC corre-
2
Complexation Studies
In comparison to the organotin-substituted crown ether lation experiment showing a 5J coupling of the o-phenyl
2, the 13C NMR spectrum of its sodium complex 2a shows protons to the rhodanide carbon atom. The binding of the
low-field shifts of approximately 2 ppm for the crown ether sodium cation to the crown ether oxygen atoms is clearly
carbon resonances. The same effect was observed for the evidenced by similar high-frequency shifts of the 13C reso-
13C NMR spectrum (CDCl3/CD3CN, 4:1) of the chlorodi- nances for the crown ether carbon atoms as observed for
phenylstannyl-substituted crown ether 4 to which 1 mol- the sodium complex 2a (see above).
equiv. of sodium tetraphenylborate (NaBPh4) had been
These results unambiguously prove that the chlorodi-
added. This clearly indicates complexation of the sodium phenylstannyl-substituted crown ether 4 is a ditopic recep-
cation by the crown ether. The 119Sn NMR spectrum of the tor simultaneously binding the sodium cation and rhodan-
same solution showed a single resonance at δ = –9.2 ppm ide anion.
indicating, as expected, no coordination of the tetraphen-
ylborate anion.
This statement obtains further support from electrospray
mass spectrometry (ESMS) and transport experiments.
The 119Sn NMR spectrum at –70 °C of a CD2Cl2 solu- Thus, the ESMS spectrum (negative mode) of a solution of
tion of the triorganotin chloride 4, to which 1 mol-equiv. the triorganotin chloride 4 to which NaSCN had been
of [(Ph3P)2N]Cl had been added, showed a single resonance added showed mass clusters at m/z = 685.14 and 766.22
at δ = –198 ppm indicating the in situ formation of the which are assigned to [5 + SCN]– and [5 + 2 SCN + Na]–,
dichlorotriorganostannate [4·Cl][(Ph3P)2N] (4a). In a sim- respectively. In the positive mode the spectrum showed a
ilar manner, addition of nBu4NSCN to a solution of the major mass cluster at m/z = 650.05 which is assigned to
triorganotin rhodanide 5 afforded, in situ, the complex [5·Na]+. Minor mass clusters at m/z = 569.07 and 609.06
[5·SCN][nBu4N] (5a). Its 119Sn NMR spectrum at –70 °C were also present which were assigned to [4 – Cl]+ and [4 –
showed a single resonance at δ = –253 ppm. The 119Sn Cl + OH + Na]+, respectively.
NMR spectrum at –70 °C of a solution of the chlorodi-
The transport properties of the chlorodiphenylstannyl-
phenylstannyl-substituted crown ether 4, to which 1 mol- substituted crown ether 4 were investigated by a U-tube ex-
equiv. of Bu4NSCN had been added, showed three reso- periment (Figure 3).
nances at δ = –198 ppm (signal a, integral 18), –216 ppm
(signal b, integral 69) and –253 ppm (signal c, integral 13).
Addition of a further 3 mol-equiv. of Bu4NSCN changed
the integral ratios of signals (a), (b) and (c) to 9, 69, and
21, respectively. Signals (a) and (c) are assigned to 4a and
5a, respectively, whereas signal (b) is tentatively assigned to
[4·SCN][nBu4N] (4b). The latter assignment is supported by
the observation of the same 119Sn chemical shift of a
CD2Cl2 solution of the triorganotin rhodanide 5 to which
1 mol-equiv. of [(Ph3P)2N]Cl had been added, and by the
fact that organostannate complexes of type [R3SnXY]– are
more stable than their corresponding symmetrically substi-
tuted derivatives [R3SnX2]– and [R3SnY2]–.[30] The 119Sn
NMR spectra at room temperature of all the solutions men-
tioned above showed no resonances, indicating fast ex-
change between the species present in the corresponding
samples.
Figure 3. Schematic presentation of the U-tube experiment.
Figure 4 demonstrates the superior capability of com-
The 119Sn NMR spectrum at room temperature of a pound 4 over triphenyltin chloride and the unsubstituted
solution of the triorganotin chloride 4 in CD2Cl2 to which 15-benzocrown-5 to transport NaSCN from an aqueous
Eur. J. Inorg. Chem. 2005, 2881–2887
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G. Reeske, M. Schürmann, B. Costisella, K. Jurkschat
FULL PAPER
as shown in Figure 3. The conductivity was determined with an
apparatus of the type LF530 from the company Wissenschaftlich-
Technische Werkstätten. The cell was calibrated at 20 °C with an
NaCl standard solution. The rhodanide transported to the aqueous
layer was identified by reaction with iron(iii).
phase through a dichloromethane layer into another aque-
ous phase. This apparently becomes possible by the simulta-
neous complexation of the sodium cation and the rhodan-
ide anion by the ditopic host 4.
Complexation Studies: The samples for 1H, 13C and 119Sn NMR
spectroscopy were prepared by dissolving the triorganotin chloride
4
(ca. 80 mg) and the corresponding amounts of NaBPh4,
nBu4NSCN and NaSCN in deuterated solvents. The 1H
(400.1 MHz) and 13C (100.6 MHz) spectra were recorded at 303 K
whereas the 119Sn (149.4 MHz) NMR spectra were recorded at
both 303 and 208 K. NaSCN was dried in vacuo (10–3 Torr) at
100 °C for several days and stored under nitrogen. NaBPh4 and
nBu4NSCN were stored in a desiccator.
Crystallography: Crystals of 2a were grown from ethanol and of
4·H2O from a CH2Cl2/Et2O solution at –5 °C. Crystallographic
data are collected in Table 3. Intensity data for the colorless crystals
were collected with a Nonius KappaCCD diffractometer with
graphite-monochromated Mo-Kα radiation. The data collections
covered almost the whole sphere of the reciprocal space with 2 (2a),
4 (4·H2O) sets at different κ angles and 203 (2a), 424 (4·H2O)
frames by ω-rotation (Δ/ω = 1°) at 2×90 s (2a), 70 s (4·H2O) per
frame. Crystal decay was monitored by repeating the initial frames
at the end of the data collection. After analysis of the duplicate
reflections, there was no indication of any decay. The structures
were solved by direct methods (SHELXS97[32]) and successive dif-
ference Fourier syntheses. Refinement applied full-matrix least-
squares methods (SHELXL97[33]). The H atoms were placed in ge-
ometrically calculated positions using a riding model with Uiso con-
strained at 1.2 times Ueq of the carrier C atom, whereas the H
atoms [H(6W1), H(6W1)] (4·H2O) bonded to the water molecule
O(6W) were located in the difference Fourier map and refined iso-
tropically. In 2a there are two C atoms disordered over two sites
with occupancies of 0.5 [C(42), C(43), C(43Ј), C(44Ј)], whereas
C(43Ј) is refined isotropically. In 4·H2O one Cl atom of the solvent
molecule CH2Cl2 is disordered over two sites with occupancies of
0.9 [Cl(3) and 0.1 Cl(3Ј)]. Atomic scattering factors for neutral
atoms and real and imaginary dispersion terms were taken from
ref.[34] The figures were created by SHELXTL.[35] CCDC-248340
(2a) and -248341 (4·H2O) contain the supplementary crystallo-
graphic 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.
Figure 4. Plot of the electric conductivity vs. time illustrating the
different ability of the triorganotin chloride 4, triphenyltin chloride,
and the unsubstituted crown ether benzo-15-crown-5 to transport
sodium rhodanide through a dichloromethane layer. The concen-
tration of 4, Ph3SnCl as well as that of the crown ether was 0.0268
mol/L.
Conclusions
Linking a chlorodiorganostannyl moiety via a dimethyl-
ene spacer with a crown ether was shown to provide the
robust ditopic host 4 for the complexation of sodium rhod-
anide. It even serves for the efficient extraction of the latter
from an aqueous solution. Given the large variety of crown
ethers and related compounds such as azacrowns and cryp-
tands on the one hand and the experience with mono- bi-
and multicentered organometal-based Lewis acids on the
other, the concept of combining representatives of these
classes of compounds in one molecule appears to be prom-
ising for designing tailor-made hosts for the complexation
of any salt.
Experimental Section
General Methods: All solvents were purified by distillation under
nitrogen from appropriate drying agents. The hydrostannylation
was carried out under nitrogen. 4-Vinylbenzo-15-crown-5[24,25] and
triphenyltin hydride[31] were synthesized as described in the litera-
ture. The NMR experiments were carried out with Bruker DRX
500, Bruker DRX 400, DPX 300, Varian Nova 600 and Varian
Mercury 200 spectrometers. Chemical shifts δ are given in ppm and
are referenced to the solvent peaks with the usual values calibrated
against tetramethylsilane (1H, 13C) and tetramethylstannane
[2-(6,7,9,10,12,13,15,16-Octahydro-5,8,11,14,17-pentaoxabenzocy-
clopentadec-2-yl)ethyl]triphenylstannane (2): 4-Vinylbenzo-15-
crown-5 (12.8 g, 44 mmol) and AIBN (115 mg) were added to
Ph3SnH (26.7 g, 41 mmol). The mixture was stirred at 70 °C for
12 h. After cooling to room temperature, CH2Cl2 (40 mL) was
added and the solution was filtered through Celite. The filtrate was
concentrated to give a yellow oil. The latter was purified by column
chromatography (silica gel, CH2Cl2). Elution with ethanol gave
16.9 g (60%) of 2 as a slightly yellow oil. 1H NMR (400.1 MHz,
CDCl3, 300 K): δ = 1.80 [t, 3J(1H-1H) = 7.7, 3J(1H-117/119Sn) =
(
119Sn). The numbering of the carbon atoms applied for the assign-
ment of the 13C resonances is shown in Scheme 2.
2
54.5 Hz, 3 H, Sn–CH2], 2.93 [t, 3J(1H-1H) = 7.7, J(1H-117/119Sn) =
56.9 Hz, 2 H, CH2–Ar], 3.72–3.79 [m, 8 H, H(9)–H(13)], 3.82–3.85
[m, 2 H, H(7)], 3.87–3.93 [m, 2 H, H(15)], 3.94–3.98 [m, 2 H, H(6)],
3
4.07–4.10 [m, 2 H, H(16)], 6.62 {d, J[H(1)-H(19)] = 2.0 Hz, 1 H,
3
4
H(19)}, 6.66 {dd, J[H(1)-H(19)] = 2.0, J[H(1)-H(3)] = 8.2 Hz, 1
Scheme 2.Numbering scheme for the assignment of the 13C NMR
resonances.
4
H, H(1)}, 6.73 {d, J[H(1)-H(3)] = 8.2 Hz, 1 H, H(3)}, 7.32–7.45
(m, 15 H, SnPh3) ppm. 13C{1H} NMR (100.6 MHz, CDCl3,
300 K): δ = 13.1 [1J(13C-117/119Sn) = 383 Hz, Sn–CH2], 32.0 [2J(13C-
117/119Sn) = 18 Hz, CH2–Ar], 69.1 [C(6)], 69.7 [C(16)], 69.8 [C(7)],
The ability of compound 4 to transport the rhodanide anion
through an organic phase was investigated by U-tube experiments
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Organotin-Substituted Crown Ethers for Ditopic Complexation
FULL PAPER
Table 3. Crystallographic data of 2a and 4·H2O.
2·NaSCN
4·H2O
Empirical formula
Formula mass [g/mol]
Crystal system
Crystal size
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C34H38O5Sn·NaSCN
726.40
monoclinic
0.08×0.04×0.04
P21/b
22.0800(17)
9.9015(7)
16.0185(9)
90.00
103.277(3)
90.00
3408.4(4)
4
1.416
0.864
1488
C29H35Cl3O5Sn·H2O
706.63
triclinic
0.15×0.13×0.13
¯
P1
10.6889(3)
12.1158(3)
13.1338(4)
84.0147(10)
76.4871(11)
69.7220(12)
1550.80(7)
2
γ [°]
V [Å3]
Z
ρcalcd. [mg/m3]
μ [mm–1]
F(000)
1.513
1.121
720
θ range [°]
Index ranges
2.98–25.04
–26 Յ h Յ 25
–11 Յ k Յ 11
–17 Յ l Յ 17
18544
89.0
5367/0.085
1522
3.17–25.36
–12 Յ h Յ 12
–13 Յ k Յ 14
–15 Յ l Յ 15
19140
99.8
5680/0.037
3606
No. of reflections collected
Completeness of θmax (%)
No. of independent reflections/Rint.
No. of reflections observed with [I Ͼ 2σ(I)]
No. of refined parameters
GoF(F2)
410
0.597
369
0.920
R1(F) [I Ͼ 2σ(I)]
0.0399
0.0944
0.0427
0.1006
wR2(F2) (all data)
(Δ/σ)max.
0.001
0.259/–0.219
0.001
0.826/–0.779
Largest difference peak/hole [e/Å3]
69.9 [C(15)], 70.8–71.3 [C(9)–C(13)], 114.1 [C(19)], 114.5 [C(3)], of 3 (7.46 g, 10.47 mmol) in CH3CN (100 mL). After stirring in
120.4 [C(1)], 128.4 [3J(13C-117/119Sn) = 47 Hz, Sn–Ph C(m)], 128.8
[4J(13C-117/119Sn) = 10 Hz Sn–Ph, C(p)], 137.0 [2J(13C-117/119Sn) =
darkness for 14 d, the solution was filtered. The solvent was evapo-
rated to give a light yellow oil. The latter was dissolved in CH2Cl2/
36 Hz, Sn–Ph C(o)], 138.1 [3J(13C-117/119Sn) = 55 Hz, C(2)], 138.7 Et2O (2:1) and cooled to –5 °C for several days to give 3 g (73%)
[Sn–Ph C(i)], 147.3 [C(18)], 149.1 [C(4)] ppm. 119Sn{1H} NMR
of 4 as colorless crystals. H NMR (400.13 MHz, CD2Cl2, 300 K):
1
(149.2 MHz, CH2Cl2, D2O capillary, 300 K): δ = –103 ppm. δ = 2.08 [t, J(1H-1H) = 7.8, J(1H-117/119Sn) = 59.2 Hz, 2 H, Sn–
3
2
C34H38O5Sn (645.37): calcd. C 63.3, H 5.9; found C 63.0, H 5.9.
CH2], 3.08 [t, 3J(1H-1H) = 7.8, 3J(1H-117/119Sn) = 87.8 Hz, 2 H,
CH2–Ar], 3.62–3.67 [m, 8 H, H(9)–H(13)], 3.74–3.77 [m, 2 H,
H(7)], 3.78–3.83 [m, 2 H, H(15)], 3.87–3.91 [m, 2 H, H(6)], 3.99–
4.04 [m, 2 H, H(16)], 6.67–6.75 (m, 3 H, Ar), 7.39–7.78 (m, 10 H,
Sn–Ph) ppm. 13C{1H} NMR (100.63 MHz, CD2Cl2 300 K): δ =
20.9 [1J(13C-117Sn) = 426, 1J(13C-119Sn) = 446 Hz, Sn–CH2], 31.0
[2J(13C-117/119Sn) = 23 Hz, CH2–Ar], 68.4 [C(6)], 68.8 [C(16)], 69.3
[C(7)], 69.4 [C(15)], 70.1–70.6 [C(9)–C(13)], 113.6 [C(19)], 114.0
[C(3)], 120.3 [C(1)], 128.8 [3J(13C-117/119Sn) = 59 Hz, Sn–Ph C(m)],
129.9 [4J(13C-117/119Sn) = 13 Hz Sn–Ph C(p)], 135.8 [2J(13C-
117/119Sn) = 47 Hz, Sn–Ph C(o)], 137.3 [3J(13C-117/119Sn) = 61 Hz,
C(2)], 139.6 [1J(13C-117Sn = 540, 1J(13C-119Sn) = 566 Hz, Sn–Ph
C(i)], 146.6 [C(18)], 148.3 [C(4)] ppm. 11 9Sn{1H} NMR
(111.9 MHz, CD2Cl2, 298 K): δ = 2 ppm. 119Sn{1H} NMR
(111.9 MHz, CD2Cl2, 193 K): δ = –155 ppm. C28H33ClO5Sn·H2O
(621.74): calcd. C 54.1, H 5.7; found C 53.7, H 5.7.
Iodo[2-(6,7,9,10,12,13,15,16-octahydro-5,8,11,14,17-pentaoxabenzo-
cyclopentadec-2-yl)ethyl]diphenylstannane (3): Iodine (2.78 g,
10.97 mmol) was added in small portions to a magnetically stirred
solution of 2 (7.07 g, 10.97 mmol) in CH2Cl2 (50 mL) in an ice
bath. The reaction mixture was stirred overnight. The solvent and
the iodobenzene were removed in vacuo. Addition of CH2Cl2
(20 mL), filtration and evaporation of the solvent afforded 7.46 g
(97%) of 2 as a slightly yellow oil. 1H NMR (500.13 MHz, CDCl3):
3
2
δ = 2.09 [t, J(1H-1H) = 8.0, J(1H-117/119Sn) = 52.6 Hz, 2 H, Sn–
CH2], 2.30 [t, 3J(1H-1H) = 8.0, 3J(1H-117/119Sn) = 88.5 Hz, 2 H, Ar-
CH2], 3.68–3.75 (m, 8 H, OCH2), 3.77–3.82 (m, 4 H, OCH2), 3.83–
3.88 (m, 4 H, OCH2), 3.91–3.96 (m, 4 H, OCH2), 4.01–4.07 (m, 4
H, OCH2), 6.65 (s, 1 H, Ar-H), 6.68 (s, 2 H, Ar-H), 7.30–7.50 (m,
10 H, Sn–Ph) ppm. 13C{1H} NMR (125.77 MHz, CDCl3, 300 K):
δ = 19.9 (Sn–CH2), 31.8 (CH2–Ar), 68.6–70.7 [C(6)–C(16)], 114.1
[C(3)], 114.5 [C(19)], 120.5 [C(1)], 128.6 [3J(13C-117/119Sn) = 58 Hz,
Sn–Ph C(m)], 129.7 [Sn–Ph C(p)], 135.8 [2J(13C-117/119Sn) = 47 Hz,
Sn–Ph C(o)], 136.3 [C(2)], 137.2 [Sn–Ph C(i)], 147.4 [C(18)], 148.9
[C(4)] ppm. 119Sn{1H} NMR (111.91 MHz, CH2Cl2, D2O capil-
lary): δ = –130 ppm. C24H33IO5Sn (695.17): calcd. C 48.4, H 4.8;
found C 48.3, H 4.9.
[2-(6,7,9,10,12,13,15,16-Octahydro-5,8,11,14,17-pentaoxabenzo-
cyclopentadec-2-yl)ethyl]diphenyl(thiocyanato)stannane (5): AgSCN
(8.30 g, 50.04 mmol) was added to a solution of 3 (3.50 g,
5.04 mmol) in CH3CN (150 mL). The reaction mixture was stirred
in darkness for 12 h followed by filtration from AgI and unreacted
AgSCN. The filtrate was concentrated to give a light yellow solid.
The latter was recrystallized from methanol to give 3.0 g (98%) of
Aqua Complex of Chloro[2-(6,7,9,10,12,13,15,16-octahydro-
5,8,11,14,17-pentaoxabenzocyclopentadec-2-yl)ethyl]diphenylstan-
nane (4·H2O): AgCl (3.08 g, 21.48 mmol) was added to a solution
1
5 as a colorless solid. H NMR (400.13 MHz, CD3OD, 300 K): δ
= 1.93 [t, 3J(1H-1H) = 7.5, 2J(1H-117/119Sn) = 67.3 Hz, 2 H, Sn–
Eur. J. Inorg. Chem. 2005, 2881–2887
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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G. Reeske, M. Schürmann, B. Costisella, K. Jurkschat
FULL PAPER
CH2], 3.12 [t, 3J(1H-1H) = 7.8, 3J(1H-117/119Sn) = 102.4 Hz, 2 H, Complex [nBu4N][5·SNC]: 119Sn{1H} NMR (149.2 MHz, CD2Cl2,
CH2–Ar], 3.55–4.00 (m, 16 H, CH2O), 6.65–6.90 (m, 3 H, Ar), 203 K): δ = 308 (3%), –252 (97%) ppm.
7.29–7.64 (m, 10 H, Sn–Ph) ppm. 13C{1H} NMR (150.84 MHz,
Complex [(Ph3P)2N][5·Cl]: 119Sn{1H} NMR (149.2 MHz, CD2Cl2,
CD2Cl2, 300 K): δ = 23.3 (Sn–CH2), 31.6 [2J(13C-117/119Sn) =
203 K): δ = –250 (19%), –214 (64%), –197 (17%) ppm.
28 Hz, CH2–Ar], 66.6–68.7 (CH2O), 113.1 [C(19)/C(3)], 120.8
Complex 4·NaSCN: 1H NMR (400.1 MHz, CD2Cl2, 300 K): δ =
[C(1)], 128.6 [3J(13C-117/119Sn) = 64 Hz, SnPh2 C(m)], 129.3 [SnPh2
C(p)], 135.4 [SCN, determined by HMBC experiment], 136.4
[2J(13C-117/119Sn) = 46 Hz, SnPh2 C(o)], 138.2 [SnPh2 C(i)], 138.4
[C(2)], 141.9 [C(18)], 145.6 [C(4)] ppm. 119Sn{1H} NMR
(111.9 MHz, CDCl3): δ = –180 (ν1/2 = 1930 Hz) ppm.
2
1.96 [t, 3J(1H-1H) = 8.3, J(1H-119/117Sn) = 66.0 Hz, 2 H, Sn–CH2],
3
3.10 [t, 3J(1H-1H) = 8.0, J(1H-117/119Sn) = 84.8 Hz, 2 H, CH2–Ar],
3.47–3.60 [m, 8 H, H(9)–H(13)], 3.61–3.70 [m, 4 H, H(7), H(15)],
3.80–3.92 [m, 4 H, H(6), H(16)], 6.61–6.80 (m, 3 H, Ar), 7.30–
7.79 (m, 10 H, Sn–Ph) ppm. 13C{1H} NMR (150.84 MHz, CD2Cl2,
Sodium Rhodanide Complex 2a: The triorganotin chloride 2 (1 g,
1.55 mmol) and NaSCN (0.170 g, 1.55 mmol) were dissolved in
ethanol (5 mL) and the mixture was heated at reflux for 1 h. The
reaction mixture was cooled to room temperature providing 700 mg
(62%) of 2a as colorless crystals. 1H NMR (400.1 MHz, CDCl3,
1
300 K): δ = 24.8 [1J(13C-117Sn) = 595, J(13C-119Sn) = 621 Hz, Sn–
CH2], 31.5 [2J(13C-117/119Sn) = 32 Hz, CH2–Ar], 67.2–69.2 [C(6)–
C(16)], 113.5 [C(19)], 113.6 [C(3)], 121.8 [C(1)], 128.3 [3J(13C-
117/119Sn) = 66 Hz, Sn–Ph, C(m)], 129.1 [4J(13C-117/119Sn) = 13 Hz,
Sn–Ph C(p)], 135.6 [N=C=S, 2J(13C-117/119Sn) = 59 Hz], 136.5
[2J(13C-117/119Sn) = 45 Hz, Sn–Ph C(o)], 139.2 [3J(13C-117/119Sn) =
68 Hz, C(2)], 142.7 [1J(13C-117Sn) = 716, 1J(13C-119Sn) = 751 Hz,
Sn–Ph C(i)], 144.9 [C(18)], 146.7 [C(4)] ppm. 119Sn{1H} NMR
(149.2 MHz, CD2Cl2, 298 K): δ = –225 (ν1/2 = 2013 Hz) ppm.
3
2
300 K): δ = 1.77 [t, J(1H-1H) = 8.28, J(1H-117/119Sn) = 52.2 Hz, 2
H, SnCH2], 2.93 [t, 3J(1H-1H) = 8.28, J(1H-117/119Sn) = 56.5 Hz, 2
3
H, CH2–Ar], 3.71 (m, 4 H, OCH2), 3.79 (m, 4 H, OCH2), 3.86 (m,
2 H, OCH2), 3.93 (m, 4 H, OCH2), 4.11 (m, 2 H, OCH2), 6.58 [s,
1 H, H(3)], 6.70 [s, 2 H, H(1), H(19)], 7.43–7.33 (m, 15 H, Sn–Ph)
ppm. 13C{1H} NMR (100.6 MHz, CDCl3 300 K): δ = 13.0 (Sn–
CH2), 31.8 (CH2–Ar), 69.0–66.5 [C(6)–C(16)], 112.3 [C(19)], 112.4
[C(3)], 121.0 [C(1)], 128.4 [3J(13C-117/119Sn) = 49 Hz, Sn–Ph C(m)],
128.8 [4J(13C-117/119Sn) = 11 Hz, Sn–Ph C(p)], 136.8 [2J(13C-
117/119Sn) = 35 Hz, Sn–Ph C(o)], 138.5 [C(2)], 138.7 [Sn–Ph C(i)],
144.6 [C(4)], 146.3 [C(18)] ppm. 119Sn{1H} NMR (149.2 MHz,
CDCl3): δ = –104 ppm. C35H38NNaO5SSn (726.45): calcd. C 57.7,
H 5.3, N 1.9; found C 58.0, H 5.3, N 1.9.
119Sn{1H} NMR (149.2 MHz, CD2Cl2, 203 K): δ = –248 (ν1/2
=
937 Hz) ppm. ESMS (+p): m/z = 650.1 [Ph2Sn(SCN) – C16H23O5]·
Na+. ESMS (–p): m/z = 685.1 [Ph2Sn(SCN)2 – C16H23O5]–, 766.2
[Ph2Sn(SCN)2 – C16H23O5·NaSCN]–.
Acknowledgments
We are grateful to the Deutsche Forschungsgemeinschaft and the
Fonds der Chemischen Industrie for financial support.
Complex [4·Na][BPh4]: 1H NMR (400.1 MHz, CDCl3/CD3CN, 4:1,
3
2
300 K): δ = 2.08 [t, J(1H-1H) = 7.9, J(1H-117/119Sn) = 56.8 Hz, 2
H, Sn–CH2], 3.12 [t, 3J(1H-1H) = 7.8, J(1H-117/119Sn) = 52.0 Hz, 2
3
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H(7)], 3.78–3.82 [m, 2 H, H(15)], 3.88–3.92 [m, 2 H, H(6)], 3.98–
–
4.04 [m, 2 H, H(16)], 6.76–6.80 (m, 3 H, Ar), 6.87 (m, BPh4 ), 7.02
3
–
[t, J(1H-1H) = 7.2 Hz, BPh4 ], 7.37–7.60 (m, 10 H, Sn–Ph) ppm.
13C{1H} NMR (100.63 MHz, CDCl3/CD3CN, 4:1, 300 K): δ = 20.5
(Sn–CH2), 30.3 (CH2–Ar), 66.3 [C(6)], 66.7 [C(16)], 67.2 [C(7)],
67.3 [C(15)], 67.8–68.1 [C(9)–C(13)], 112.9 [C(19)], 113.1 [C(3)],
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–
–
116.3 (BPh4 ), 121.1 [C(1)], 121.3 (BPh4 ), 124.1 (BPh4 ), 128.2
[3J(13C-117/119Sn) = 59 Hz, Sn–Ph, C(m)], 129.3 [4J(13C-117/119Sn) =
14 Hz, Sn–Ph C(p)], 135.2 [2J(13C-117/119Sn) = 43 Hz, Sn–Ph C(o)],
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–
135.4 (BPh4 ), 137.5 [C(2)], 139.2 [Sn–Ph C(i)], 144.6 [C(18)], 146.1
[C(4)], 162.7–164.2 (q, BPh4 ) ppm. 119Sn{1H} NMR (149.2 MHz,
–
CDCl3/CD3CN, 4:1, 300 K): δ = –9 ppm.
1
Complex [nBu4N][4·SCN]: H NMR (400.1 MHz, CD2Cl2, 300 K):
3
3
δ = 0.93 [t, J(1H-1H) = 8 Hz, 12 H, nBu4N+ CH3], 1.29 [q, J(1H-
1H) = 7.3 Hz, 8 H, nBu4N+ CH2], 1.45 (m, 8 H, nBu4N+ CH2),
1.91 [t, 3J(1H-1H) = 8.8, J(1H-117/119Sn) = 74.8 Hz, 2 H, Sn–CH2],
2
2.93 (m, 8 H, nBu4N+ N–CH2), 3.0 [t, 3J(1H-1H) = 8.8, 3J(1H-
117/119Sn) = 52.3 Hz, 2 H, CH2–Ar], 3.65 [s, 8 H, H(9)–H(13)], 3.75–
3.84 [m, 4 H, H(7) H(15)], 3.98–4.05 [m, 4 H, H(6) H(15)], 6.72–
6.84 (m, 3 H, Ar), 7.25–7.40 [m, 6 H, Sn–Ph H(m), H(p)], 7.84–
8.20 [m, 3J(1H-117/119Sn) = 30.6 Hz, 4 H, Sn–Ph H(o)]. 13C{1H} [16] M. T. Blanda, J. Frels, J. Lewicki, Supramol. Chem. 1998, 9,
NMR (100.63 MHz, CD2Cl2, 300 K): δ = 13.3 (nBu4N+), 19.5
(nBu4N+), 23.6 (nBu4N+), 31.5 (CH2–Ar), 58.5 (nBu4N+), 68.4
[C(6)], 69.0 [C(16)], 69.3 [C(7)], 69.4 [C(15)], 70.1–70.5 [C(9)–
C(13)], 113.9 [C(19)], 114.1 [C(3)], 120.2 [C(1)], 127.6 [3J(13C-
117/119Sn) = 64 Hz, Sn–Ph, C(m)], 128.1 [Sn–Ph C(p)], 136.7 [2J(13C-
117/119Sn) = 47 Hz, Sn–Ph C(o)], 138.9 [C(2)], 146.8 [C(18)], 148.8
[C(4)] ppm. 119Sn{1H} NMR (149.2 MHz, CD2Cl2, 300 K): no res-
onance found. 119Sn{1H} NMR (149.2 MHz, CD2Cl2, 208 K): δ
= –253 (13%), –217 (69%), –198 (18%) ppm.
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2886
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2005, 2881–2887

Organotin-Substituted Crown Ethers for Ditopic Complexation
FULL PAPER
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Published Online: June 14, 2005
Eur. J. Inorg. Chem. 2005, 2881–2887
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2887