Ph(3-n)XnSnCH2-16-crown-5 (X = F, Cl, Br, I, SCN; n = 1, 2): Intramolecular O → Sn coordination versus ditopic complexation of sodium thiocyanate

Article abstract of DOI:10.1021/om700304p

The synthesis of the organotin-substituted crown ethers Ph _(3-n)X_nSn-CH₂-16-crown-5 (1, n = 0; 2, n = 1, X = I; 3, n = 1, X = Br; 4, n = 1, X = Cl; 5, n = 1, X = F; 6, n = 1, X = SCN; 7, n = 2, X = Cl; 8, n = 2, X = I) is reported. The compounds are characterized by elemental analyses and ¹H, ¹³C, ¹⁹F, ²³Na, and ¹¹⁹Sn NMR spectroscopy and in the case of compound 4 also by ¹¹⁹Sn MAS NMR spectroscopy. Single-crystal X-ray diffraction analyses reveal for compounds 2-5 trigonal-bipyramidally configurated tin atoms with intramolecular Sn - O distances ranging between 2.530(2) (5) and 2.571(1) A (4), whereas the tin atom in compound 1 shows a distorted tetrahedral configuration. The tin atoms in compounds 7 and 8 are hexacoordinated with intramolecular Sn - O distances ranging between 2.473(1) (7) and 2.522(1) A(7). NMR spectroscopy reveals the ability of compound 4 to form, in competition with intramolecular O → Sn coordination, a ditopic complex with NaSCN.

Full text of DOI:10.1021/om700304p

4170
Organometallics 2007, 26, 4170-4179
Ph(3-n)XnSnCH2-16-crown-5 (X ) F, Cl, Br, I, SCN; n ) 1, 2):
Intramolecular O f Sn Coordination versus Ditopic Complexation
of Sodium Thiocyanate†
Gregor Reeske, Markus Schu¨rmann, Burkhard Costisella, and Klaus Jurkschat*
Lehrstuhl fu¨r Anorganische Chemie II, UniVersita¨t Dortmund, D-44221 Dortmund, Germany
ReceiVed March 28, 2007
The synthesis of the organotin-substituted crown ethers Ph(3-n)XnSn-CH2-16-crown-5 (1, n ) 0; 2, n
) 1, X ) I; 3, n ) 1, X ) Br; 4, n ) 1, X ) Cl; 5, n ) 1, X ) F; 6, n ) 1, X ) SCN; 7, n ) 2, X
) Cl; 8, n ) 2, X ) I) is reported. The compounds are characterized by elemental analyses and 1H, 13C,
19F, 23Na, and 119Sn NMR spectroscopy and in the case of compound 4 also by 119Sn MAS NMR
spectroscopy. Single-crystal X-ray diffraction analyses reveal for compounds 2-5 trigonal-bipyramidally
configurated tin atoms with intramolecular Sn-O distances ranging between 2.530(2) (5) and 2.571(1)
Å (4), whereas the tin atom in compound 1 shows a distorted tetrahedral configuration. The tin atoms in
compounds 7 and 8 are hexacoordinated with intramolecular Sn-O distances ranging between 2.473(1)
(7) and 2.522(1) Å (7). NMR spectroscopy reveals the ability of compound 4 to form, in competition
with intramolecular O f Sn coordination, a ditopic complex with NaSCN.
which got started almost simultaneously in the late 1960s, with
that of anion recognition but which developed much faster to
the extent that the Nobel Prize was awarded in 1987 to their
front leaders Pedersen, Lehn, and Cram.
One challenge for chemists that originates as a logical
consequence from the two subdisciplines of ion recognition is
the combination of both cation and anion binding sites in one
molecule in order to create a heteroditopic receptor, which, for
instance, should make possible the selective recognition and/or
extraction of particular salts. This concept was shown to be
successful, and a variety of heteroditopic hosts for salts have
been reported to date.24-29
Among these, only a few organoelement species are known
such as the boron- and organotin-substituted crown ethers A,30,31
B,32 and C,33 respectively (Chart 1). The former binds potassium
fluoride, KF, as an associated ion pair, whereas compound B is
a straightforward example of a host molecule that binds sodium
thiocyanate, NaSCN, as separate ions. This ability of compound
B is remarkable because ion separation requires energy to
Introduction
The design of molecular hosts for selective recognition of
anions has become a rather popular topic of contemporary
chemical research, and this is manifested by a plethora of
publications. The progress made in this field has been regularly
reviewed over the years.1-23 These studies complement in an
ideal manner the rich chemistry of selective cation receptors,
* Corresponing author. E-mail: klaus.jurkschat@uni-dortmund.de.
Fax: +49(0)231-5048.
† Dedicated to Prof. Joachim Heinicke on the occasion of his 60th
birthday. This work contains part of the Ph.D. Thesis of G.R., Dortmund
University, 2004. Parts of this work were first presented at the XI
International Conference on the Coordination and Organometallic Chemistry
of Germanium, Tin, and Lead, Santa Fe, NM, June 27-July 2, 2004, Book
of Abstracts, p 26.
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10.1021/om700304p CCC: $37.00 © 2007 American Chemical Society
Publication on Web 07/13/2007

Ph(3-n)XnSnCH2-16-crown-5 (X ) F, Cl, Br, I, SCN; n ) 1, 2)
Organometallics, Vol. 26, No. 17, 2007 4171
Chart 1
Figure 1. Molecular structure of 1 showing 30% probability
displacement ellipsoids and the crystallographic numbering scheme.
Chart 2
Table 1. Selected Bond Distances (Å) for Compounds 1-5
1
2
3
4
5
X ) C(13) X ) I(1) X ) Br(1) X ) Cl(1) X ) F(1)
Sn(1)-C(1) 2.132(2) 2.149(3) 2.140(2)
Sn(1)-C(7) 2.158(2) 2.136(3) 2.146(2)
Sn(1)-X
2.131(2) 2.136(3)
2.144(2) 2.142(3)
2.153(2) 2.8220(3) 2.6088(4) 2.4541(5) 2.0147(15)
overcome the Coulomb forces. However, both compounds A
and B are unstable under noninert conditions, which limits their
potential applications. With this in mind we have synthesized
the more robust organotin-substituted crown ether C, in which
the organotin moiety is linked to the crown ether via a
dimethylene spacer. As it was demonstrated by a U-tube
experiment, compound C is able to transport sodium thiocyanate
from aqueous solution through a dichloromethane phase into
an aqueous phase.
In continuation of our systematic studies on organotin-
substituted crown ethers33 we report here compounds of type
D (Chart 2) and investigate the complexation behavior of one
representative (n ) 1, X ) Cl) toward [(Ph3P)2N]+Cl-, n-Bu4-
NSCN, NaBPh4, NaI, NaCl, and NaSCN.
Sn(1)-C21 2.161(2) 2.128(3) 2.129(2)
2.131(2) 2.136(2)
2.571(1) 2.5301(18)
Sn1-O1
Sn1-O5
4.990(1) 2.554(2) 2.564(2)
3.206(1)
Reaction in CH2Cl2 under ice cooling of the tetraorganostan-
nane 1 with 1 molar equiv of iodine and bromine almost
quantitatively gave the corresponding triorganotin iodide 2 and
the triorganotin bromide 3, respectively. Treatment of 2 with
an excess of AgCl in CH3CN afforded the triorganotin
chloride 4, whereas reaction with n-Bu4NF‚3H2O in CH2Cl2
provided the triorganotin fluoride 5. Finally, reaction of
the triorganotin iodide with AgSCN gave the triorganotin
thiocyanate 6 (Scheme 1).
Compounds 1-6 are colorless to slightly yellow (2) crystal-
line solids, which are well soluble in common organic solvents
such as CH2Cl2, CHCl3, and thf.
Results and Discussion
As a representative of the triorganotin halides 2-5 the
molecular structure of the triorganotin chloride 4 is shown in
Figure 2. The structures of compounds 2, 3, and 5 are rather
similar, and they are given in the Supporting Information
(Figures S1-S3). Selected geometrical parameters of com-
pounds 2-5 are collected in Tables 1 and 2.
Synthetic Aspects and Molecular Structures in the Solid
State. The reaction of 15-methylene-1,4,7,10,13-pentaoxa-
cyclohexadecane34 with triphenyltin hydride provided the triph-
enytin-substituted crown ether 1 (eq 1). The molecular structure
The tin atoms in compounds 2-5 show distorted trigonal
bipyramidal configurations (geometrical goodness ∆Σ(ϑ)36 63°
(2), 64° (3, 4, and 5)) with the carbon atoms C(1), C(7), and
C(21) occupying the equatorial and the halogen atoms (I(1) (2),
Br(1) (3), Cl(1) (4), F(1) (5)) and the oxygen atom O(1)
occupying the axial positions. The Sn(1) atom is displaced by
0.152(2) (2), 0.588(1) (3), 0.269(1) (4), and 0.266(2) (5) Å from
the plane defined by C(1), C(7), and C(21) in the direction of
the corresponding halogen atom. The intramolecular Sn(1)-
O(1) distances differ only slightly and fall in the range between
2.530(2) (5) and 2.571(1) (4) Å. They are comparable with
Sn-O distances found in other intramolecularly coordinated
triorganotin halides containing five-membered chelates.37-40 As
of compound 1 is shown in Figure 1, and selected bond distances
and bond angles are listed in Table 1.
The tin atom in the tetraorganotin compound 1 adopts a
monocapped-tetrahedral configuration with the O(5) atom being
the capping atom. The latter approaches the tin atom via
the tetrahedral face defined by C(1), C(13), and C(21) at a
Sn(1)‚‚‚O(5) distance of 3.206(1) Å, shorter than the sum of
the van der Waals radii35 of oxygen (1.50 Å) and tin (2.20 Å).
The Sn(1) atom is displaced by 0.5593(9) Å out of this plane
in the direction of C(7).
(36) Kolb, U.; Beuter, M.; Dra¨ger, M. Inorg. Chem. 1994, 33, 4522.
(37) Fu, F. Z.; Li, H. Y.; Zhu, D. S.; Fang, Q. X.; Pan, H. A.; Tiekink,
E. R. T.; Kayser, F.; Biesemans, M.; Verbruggen, I.; Willem, R.; Gielen,
M. J. Organomet. Chem. 1995, 490, 163.
(38) Kayser, F.; Biesemans, M.; Delmotte, A.; Verbruggen, I.; Deborger,
I.; Gielen, M.; Willem, R.; Tiekink, E. R. T. Organometallics 1994, 13,
4026.
(34) Tomoi, M.; Abe, O.; Ikeda, M.; Kihara, K.; Kakiuchi, H. Tetrahe-
dron Lett. 1978, 3031.
(35) Bondi, A. J. Phys. Chem. 1964, 68, 441.
(39) Jambor, R.; Dostal, L.; Ruzicka, A.; Cisarova, I.; Brus, J.; Holcapek,
M.; Holecek, J. Organometallics 2002, 21, 3996.

4172 Organometallics, Vol. 26, No. 17, 2007
Reeske et al.
a
Scheme 1
a
Conditions: (i) AgCl (excess), CH3CN, -AgI; (iia) for Y ) F: n-Bu4NF (excess), CH2Cl2, -n-Bu4NI; (iib) for Y ) SCN: AgSCN, -AgI;
(iii) HCl(g), CH2Cl2, -78 °C, -C6H6; (iv) 2 I2, CH2Cl2, 0 °C, -2 PhI.
Figure 3. Molecular structure of 7 showing 30% probability
displacement ellipsoids and the crystallographic numbering scheme.
Figure 2. Molecular structure of 4 showing 30% probability
displacement ellipsoids and the crystallographic numbering scheme.
expected, the tin-halogen distances are longer than the corre-
sponding distances in tetracoordinated triorganotin halides,
with this effect being least pronounced for the triorganotin
fluoride 5.
Two-fold functionalization at the tin atom was achieved by
reaction of the tetraorganostannane 1 with gaseous hydrogen
chloride to give the diorganotin dichloride 7, and with 2 molar
equiv of iodine to give the diorganotin diiodide 8 (Scheme 1).
Both compounds 7 and 8 are crystalline solids, but in contrast
to the triorganotin halides 2-5, they exhibit lower solubility in
organic solvents.
The molecular structures of the diorganotin dihalides 7 and
8 are shown in Figures 3 and 4, respectively, and selected
geometrical parameters are collected in Tables 3 and 4. The tin
atoms in compounds 7 and 8 are each hexacoordinated by two
carbon, two oxygen, and two halogen atoms (Cl for 7, I for 8),
with an overall distorted octahedral trans-cis-cis configuration.
The distortion is mainly the result of ligand constraint and
Figure 4. Molecular structure of 8 showing 30% probability
displacement ellipsoids and the crystallographic numbering scheme.
especially manifested in (i) the decrease of the C(1)-Sn(1)-
C(11) angles from 180° to 151.44(6)° for 7 and 150.5(2)° for
8, (ii) the decrease of the O(1)-Sn(1)-O(5)/O(1A) angles from
90° to 74.11(0)° for 7 and 73.9(1)° for 8, and (iii) the increase
of the Cl(1)-Sn(1)-Cl(2) and I(1)-Sn(1)-I(1A) angles from
(40) Munguia, T.; Lopez-Cardoso, M.; Cervantes-Lee, F.; Pannell, K.
H. Inorg. Chem. 2007, 46, 1305.

Ph(3-n)XnSnCH2-16-crown-5 (X ) F, Cl, Br, I, SCN; n ) 1, 2)
Organometallics, Vol. 26, No. 17, 2007 4173
Table 2. Selected Bond Angles (deg) for Compounds 1-5
1
2
3
4
5
X ) C(13)
X ) I(1)
X ) Br(1)
X ) Cl(1)
X ) F(1)
C(7)-Sn(1)-C(1)
C(21)-Sn(1)-C(1)
C(21)-Sn(1)-C(7)
C(1)-Sn(1)-O(1)
C(7)-Sn(1)-O(1)
C(21)-Sn(1)-O(1)
C(1)-Sn(1)-X
108.29(6)
110.29(6)
101.31(6)
114.2(1)
121.1(1)
119.8(1)
90.0(1)
86.03(9)
72.5(1)
100.26(8)
97.57(8)
94.49(8)
166.45(5)
110.4(2)
131.5(2)
114.8(2)
112.86(8)
119.55(9)
122.93(8)
87.79(7)
88.79(7)
72.79(7)
97.03(6)
98.54(6)
96.09(6)
168.82(3)
109.0(1)
124.5(1)
114.1(2)
112.33(7)
119.76(7)
123.21(7)
87.98(6)
88.63(6)
72.75(5)
97.15(5)
98.05(5)
96.53(5)
169.26(3)
108.96(9)
124.3(1)
114.3(1)
110.92(9)
121.62(10)
122.84(9)
86.50(8)
88.16(8)
74.86(8)
96.26(8)
95.43(8)
99.50(8)
174.34(6)
106.88(14)
124.29(15)
112.02(17)
C(7)-Sn(1)-X
106.04(6)
120.88(6)
C(21)-Sn(1)-X
O(1)-Sn(1)-X
C(23)-O(1)-Sn(1)
C(24)-O(1)-Sn(1)
C(22)-C(21)-Sn(1)
119.8(1)
Table 3. Selected Bond Distances (Å) for Compounds 7 and
8
Chart 3
7
8
X(1) ) Cl(1), X(2) ) Cl(2), X(1) ) I(1), X(2) ) I(1a),
X(3) ) O(5)
X(3) ) O(1a)
Sn(1)-X(1)
Sn(1)-X(2)
Sn(1)-C(1)
Sn(1)-C(11)
Sn(1)-O(1)
Sn(1)-O(5)
2.4234(4)
2.4240(4)
2.128(2)
2.123(2)
2.522(1)
2.4793(9)
2.8050(3)
2.137(4)
2.123(5)
2.482(2)
the 119Sn NMR chemical shifts of δ -130 (2), -96 (3), -88
(4), -106 [1J(119Sn-19F) 2207 Hz] (5), -125 (7), and -266
(8) being low-frequency shifted with respect to related com-
pounds having comparable substituent patterns at the tin atoms
but lack any intramolecular or intermolecular coordination, such
as the diphenylmethyltin iodide Ph2MeSnI (δ -68),42 the
Table 4. Selected Bond Angles (deg) for Compounds 7 and 8
7
8
X(1) ) Cl(1),
X(2) ) Cl(2),
X(3) ) O(5)
X(1) ) I(1),
X(2) ) I(1a),
X(3) ) O(1a)
1
triorganotin fluoride Ph2(Me3SiCH2)SnF (δ 25, J(119Sn-19F)
2380 Hz),43 the diphenylethyltin chloride Ph2EtSnCl
(δ 17),44 the 1,2-bis(diphenylhalostannyl)ethanes (Ph2-
XSnCH2)2, (X ) I, δ -54; X ) Br, δ -5; X ) Cl, δ 2),44 the
bis(dichlorophenylstannyl)methane (PhCl2Sn)2CH2 (δ 8),45
and the 1,2-bis(diiodophenylstannyl)ethane (PhI2SnCH2)2 (δ
-169).44 Moreover, the 119Sn chemical shift for compound 4
(δ -88) is essentially temperature-independent (between 20 and
-80 °C) and rather close to the 119Sn MAS NMR chemical
shift of δ -73.
C(11)-Sn(1)-C(1)
C(1)-Sn(1)-X(1)
C(11)-Sn(1)-X(1)
C(1)-Sn(1)-X(2)
C(11)-Sn(1)-X(2)
X(1)-Sn(1)-X(2)
C(1)-Sn(1)-O(1)
C(11)-Sn(1)-O(1)
X(1)-Sn(1)-O(1)
X(2)-Sn(1)-O(1)
X(3)-Sn(1)-O(1)
C(1)-Sn(1)-O(5)
C(11)-Sn(1)-O(5)
X(1)-Sn(1)-O(5)
X(2)-Sn(1)-O(5)
C(13)-O(1)-Sn(1)
C(14)-O(1)-Sn(1)
C(21)-O(5)-Sn(1)
C(22)-O(5)-Sn(1)
C(12)-C(11)-Sn(1)
151.44(6)
98.72(4)
99.47(4)
98.22(4)
100.67(4)
98.44(2)
84.80(4)
71.55(5)
96.05(3)
164.55(3)
74.11(3)
85.92(4)
72.60(5)
168.79(3)
90.94(2)
110.55(8)
129.09(8)
128.66(8)
111.13(8)
108.2(1)
150.5(2)
99.51(8)
100.05(9)
96.33(1)
84.4(1)
72.2(1)
94.63(5)
73.9(1)
1
Exemplarily, compound 4 was studied in more detail by H
and 13C NMR spectroscopy. The 13C spectrum (CDCl3) at room
temperature of the triorganotin chloride 4 displayed only six
resonances for the crown ether carbon atoms, indicating, on the
13C NMR time scale, a symmetric structure 4b with pairs of
equivalent carbon atoms C6/C8, C5/C9, C3/C11, C2/C12, and
C14/C16 rather than an unsymmetrical structure 4a (Charts 3,
4).
111.3(2)
127.1(2)
108.3(3)
This view is supported by a 1H-13C-HSQC experiment
showing only one resonance for the C14 and C16 carbon atoms.
No decoalescence of these signals was observed at -80 °C.
Worth mentioning is the 119Sn NMR spectrum of the
triorganotin thiocyanate 6 (see Supporting Information). It shows
90° to 98.44(2) (7) and 96.33(1)° (8). The intramolecular Sn-
(1)-O(1) and Sn(1)-O(5) distances of 2.522(1) and 2.4793(9)
Å in the diorganotin dichloride 7 and the Sn(1)-O(1) distance
of 2.482(2) Å in the diorganotin diiodide 8 are slightly shorter
than the corresponding distances in the triorganotin halides 2-5
(see above).
Structures in Solution. The tin atom in compound 1 is
essentially tetracoordinated, as expected. It shows a 119Sn NMR
chemical shift of δ -110, which is close to δ -92 found for
Ph3SnMe.41
1
a triplet resonance (δ -155, J(119Sn-14N) 141 Hz) as result
of 119Sn-14N coupling and indicates a rather symmetric electron
distribution in the SCN-Sn moiety. The 14N NMR spectrum
(see Supporting Information) exhibits a singlet resonance at δ
-236 (ν1/2 ) 65 Hz).
The intramolecular Sn-O coordination found in the solid state
for the triorganotin halides 2-5 and the diorganotin dihalides
7 and 8, respectively, is retained in solution, as evidenced by
(42) Gielen, M.; Jurkschat, K. J. Organomet. Chem. 1984, 273, 303.
(43) Dakternieks, D.; Jurkschat, K.; Zhu, H.; Tiekink, E. R. T. Orga-
nometallics 1995, 14, 2512.
(44) Jurkschat, K.; Hesselbarth, F.; Dargatz, M.; Lehmann, J.; Kleinpeter,
E.; Tzschach, A.; Meunier-Piret, J. J. Organomet. Chem. 1990, 388, 259.
(45) Dakternieks, D.; Jurkschat, K.; Wu, H.; Tiekink, E. R. T. Organo-
metallics 1993, 12, 2788.
(41) Davies, A. G.; Harrison, P. G.; Kennedy, J. D.; Mitchell, T. N.;
Puddephatt, R.; McFarlan, W. J. Chem. Soc. A 1969, 1136.

4174 Organometallics, Vol. 26, No. 17, 2007
Reeske et al.
Scheme 2
Scheme 3
Scheme 4
Complexation Studies. The 119Sn NMR spectrum at -40 °C
of a solution of the triorganotin chloride 4 in CD2Cl2 to which
had been added 1 molar equiv of sodium tetraphenyloborate,
NaBPh4, displayed one resonance at δ 13 (ν1/2 ) 207 Hz), which
-
is assigned to the sodium complex [4‚Na]+BPh4 in which no
O f Sn coordination takes place and in which the tin atom is
four-coordinate. In addition to the 119Sn NMR chemical shift,
the latter statement is supported by a decrease of both the 2J(1H-
1
119Sn) and J(13C-119Sn) couplings to 47 and 434 Hz, respec-
tively, as compared with 72 and 548 Hz measured for the
triorganotin chloride 4. No 119Sn NMR signal was observed at
room temperature. Apparently, there is an equilibrium in which
the Lewis acidic sodium cation and tin atom compete for the
oxygen Lewis bases (Scheme 2). The equilibrium becomes slow
at low temperature and shifts to the right. That the sodium cation
is indeed coordinated by the crown ether oxygen atoms is
supported by (i) the high-frequency shift of the 13C resonance
for the C14/C16 crown ether carbon atoms from δ 74.4 to δ
78.1 and the low-frequency shift of the 13C signals for the C2-
C12 carbon atoms by approximately 0.4 ppm (for numbering
see Chart 4 in the Experimental Section) and (ii) by the 23Na
NMR spectrum (CDCl3/CD3CN, 4:1) showing a rather broad
resonance at δ 1.94 (ν1/2 573 Hz) in comparison to the sharp
resonance at δ 1.84 (ν1/2 71 Hz) observed in the absence of
compound 4. In CD2Cl2 solution of [4‚Na]+BPh4-, an even
broader signal at δ 1.40 (ν1/2 2232 Hz) was observed. Line
broadening is a typical measure for the identification of crown
ether complexes with sodium cations, whereas the 23Na chemical
shifts do not vary dramatically between free and complexed
sodium cation.46
(ii) a change in the integral ratio of signals d and e to 47:53.
The results are interpreted in terms of an equilibrium between
the triorganotin chloride 4 (represented by signal d) and its
triorganodichlorostannate complex [4‚Cl]-[(Ph3P)2N]+ (repre-
sented by signal e) (Scheme 3) with, on the 119Sn NMR time
scale, the equilibrium being fast at ambient temperature and
slow at -70 °C.
Interestingly, the thiocyanate anion, as its tetrabutylammo-
nium salt, is not able to break the OfSn coordination in the
triorganotin chloride 4; that is, the 119Sn NMR spectrum of a
solution of 4 in CDCl3 to which had been added 1 molar equiv
of n-Bu4NSCN displayed a sharp resonance at δ -88, identical
with the signal observed for a solution of pure 4.
In order to check whether the 119Sn NMR spectrum mentioned
above can indeed be interpreted in terms of formation of
[4‚Na]+BPh4 (Scheme 2) and not with formation of the
-
So far, we learned that the sodium cation as well as the
chloride anion, as their soluble salts with appropriate counter-
ions, are able to break the intramolecular OfSn coordination
in the triorganotin chloride 4. However, the complexation ability
of 4 is not strong enough to overcome the lattice energy of
sodium chloride (790 kJ/mol)47 and to solubilize the latter to
give a ditopic zwitterionic complex [4‚NaCl]; that is, no reaction
was observed upon addition of NaCl to a solution of compound
4 in CDCl3. The lattice energy of sodium iodide is lower and
amounts to 705 kJ/mol.47 The 119Sn NMR spectrum at room
temperature of a solution of compound 4 in CD2Cl2 to which
had been added 1 molar equiv of NaI displayed two broad
resonances at -87 (ν1/2 454 Hz, integral 41, 4) and -129 (ν1/2
794 Hz, integral 59, 2). At -70 °C both signals sharpened but
did not significantly change their integral ratio. The 119Sn NMR
spectrum of compound 4 in CD2Cl2 that had been reacted with
excess NaI and from which the precipitate had been filtered
showed a single resonance at δ -61. This signal is assigned to
the homotopic complex [2‚Na]+I- (Scheme 4), containing a
four-coordinate tin atom (see δ -68 of tetracoordinated Ph2-
MeSnI for comparison). This assignment is supported by the
triorganotin cation [Ph2Sn-CH2-16-crown-5]+, tetraphenylobo-
rate anion BPh4-, and NaCl, we reacted compound 2 with
AgClO4 in CH3CN and, after the AgI had been filtered and the
CH3CN had been removed in vacuo, obtained a colorless oil.
The 119Sn NMR spectrum in CDCl3 of this oil displayed a single
resonance at δ -71. With caution, we assign this signal to [Ph2-
Sn-CH2-16-crown-5]+ClO4-. Under the assumption that ex-
change of a perchlorate anion by a tetraphenyloborate anion
will have only little influence on the 119Sn chemical shift, this
result confirms our interpretation concerning Scheme 2.
The 119Sn NMR spectrum (CD2Cl2) at ambient temperature
of a solution of the triorganotin chloride 4 to which had been
added 1 molar equiv of [(Ph3P)2N]+Cl- showed a broad
resonance at δ -121 (integral 96, ν1/2 970 Hz, signal c). At
-70 °C two sharp resonances were observed at δ -89 (integral
65, signal d) and -199 (integral 35, signal e). Addition of a
second molar equivalent of [(Ph3P)2N]+Cl- causes (i) signal c
to broaden further (ν1/2 2300 Hz) and to shift to δ -140 and
(46) (a) Grotjahn, M.; Lehmann, S.; Aurich, J.; Holdt, H. J.; Kleinpeter,
E. J. Phys. Org. Chem. 2001, 14, 43. (b) Gierczyk, B.; Schroeder, G.;
Wojciechowski, G.; Rosalski, B.; Brzezinski, B.; Zundel, G. Phys. Chem.
Chem. Phys. 1999, 1, 4897. (c) Karkhaneei, E.; Zebarjadian, M. H.;
Shamsipur, M. J. Inclusion Phenom. Macrocyclic Chem. 2006, 54, 309.
(47) Lide, D. R. In Handbook of Chemistry and Physics, 81st ed.; CRC
Press: New York, 2000-2001.

Ph(3-n)XnSnCH2-16-crown-5 (X ) F, Cl, Br, I, SCN; n ) 1, 2)
Organometallics, Vol. 26, No. 17, 2007 4175
Scheme 5
Notably, the equilibrium mixture as shown in Scheme 5 was
also formed upon addition of an equimolar amount of sodium
chloride to the solution of the triorganotin thiocyanate 6 in
CDCl3. However, it took the mixture 8 days to reach equilib-
rium, indicating kinetic control of the complexation.
The 119Sn NMR spectrum (CDCl3) of the triorganotin
thiocyanate 6 to which had been added 1 molar equiv of sodium
thiocyanate displayed two resonances at δ -155 (ν1/2 418 Hz,
integral 62) and -225 (ν1/2 154 Hz, integral 38), respectively,
indicating the equilibrium shown in Scheme 6. The latter signal
is assigned with caution to the ditopic complex [6‚NaSCN]. The
equilibrium is further supported by observation of two 13C
resonances for the SnCH2 carbons at δ 18.9 and 23.0,
respectively, being assigned to 6 and [6‚NaSCN].
Notably, measuring the 119Sn NMR spectrum of the same
sample 10 days later revealed complete formation of [6‚NaSCN]
(only one sharp resonance at δ -225) and again indicates kinetic
control of the complexation process.
Scheme 6
Conclusion
A variety of organotin-substituted crown ethers were prepared,
the design of which allows intramolecular OfSn coordination.
Nevertheless, as it was shown exemplarily for the chlorodiphe-
nylstannyl-substituted compound 4 in solution, this intramo-
lecular OfSn coordination is broken by addition of a chloride
anion (as its [(Ph3P)2N]+ salt) or sodium cation (as its Ph4B-
salt), as well as by addition of sodium chloride or sodium
thiocyanate, thus forming the corresponding ditopic complex
[4‚NaSCN] or [6‚NaSCN]. Most interestingly, the latter process,
that is, the dissolution of these salts, is kinetically controlled
and might even take several days.
These results are promising, as they support the validity of
the general concept for ditopic salt complexation and encourage
future efforts for the design of related organometal-substituted
crown compounds. One strategy to enable complexation of salts
such as sodium or potassium fluoride having a high lattice
energy should be to increase the Lewis acidity of the anion
binding site and not allow the crown ether-oxygen atoms to
interact with this Lewis acid.
13C NMR spectrum with the C14/C16 resonance being shifted
to δ 77.6 and the 1H NMR spectrum unambiguously indicating
sodium ion coordination. Apparently, the Lewis acidity of the
tin atom in [2‚Na]+I- (Scheme 4) is not high enough to induce
charge separation under formation of a triorganodiiodostannate
complex. Addition of tetrabutylammonium fluoride trihydrate,
n-Bu4NF‚3H2O, to the solution caused precipitation of sodium
fluoride and quantitative formation of the triorganotin iodide 2
(Scheme 4).
Sodium thiocyanate, NaSCN, has an even lower lattice energy
of 682 kJ/mol.47 The 119Sn NMR spectrum at room temperature
of a solution of compound 4 in C2D2Cl4 to which had been
added 1 molar equiv of NaSCN displayed three broad reso-
nances at δ -89 (ν1/2 219 Hz, integral 43, signal f, 4), δ -157
(ν1/2 325 Hz, integral 18, signal g), and δ -229 (ν1/2 219 Hz,
integral 39, signal h), respectively. Lowering the temperature
to -20 °C caused the signals to sharpen and their integral ratio
to change slightly (f:g:h ) 48:14:38). Changing the molar ratio
of 4:NaSCN from 1:1 to 1:2 caused a change of the integral
ratio of the signals as well (f:g:h ) 41:10:49).
Experimental Section
General Methods. All solvents were purified by distillation
under nitrogen atmosphere from the appropriate drying agents. The
hydrostannylation was carried out under nitrogen atmosphere. 15-
Methylene-1,4,7,10,13-pentaoxacyclohexadecane34 and triphenyltin
hydride48 were synthesized as described in the literature. The NMR
experiments were carried out on a Bruker DRX 400, Bruker DPX
300, Varian Mercury 200, or Varian Inova 600 spectrometer. NMR
experiments are carried out at ambient temperature unless a different
temperature is given. Chemical shifts (δ) are given in ppm and are
referenced to the solvent peaks with the usual values calibrated
against tetramethylsilane (1H, 13C), CFCl3 (19F), NaCl solution in
D2O (23Na), CH3NO2 (14N), and tetramethylstannane (119Sn). The
numbering scheme for the crown ether moiety is pictured in
Chart 4.
The signal at δ -157 is assigned to the triorganotin
thiocyanate Ph2(NCS)Sn-CH2-16-crown-5 (6), with the assign-
ment being confirmed by addition of the authentic compound.
The signal at δ -229 can be assigned with caution to the ditopic
complex [4‚NaSCN] or [6‚NaSCN] (Scheme 5). Given the
smaller difference between the 119Sn chemical shift observed
(signal h) and that of compound 6 (72 ppm) and compound 4
(140 ppm), respectively, and the result shown in Scheme 6 (see
below), the assignment of signal h to [6‚NaSCN] is favored.
The electrospray ionization mass spectrum (positive mode) of
the authentic solution displayed mass clusters centered at m/z
602.2, 579.2, and 521.2 which are assigned to [Ph2(NCS)Sn-
CH2-16-crown-5‚Na]+, [Ph2ClSn-CH2-16-crown-5‚Na]+, and
[Ph2Sn-CH2-16-crown-5]+, respectively, whereas the spectrum
of pure compound 4 showed only the two latter mass clusters.
The existence of three different species being in equilibrium
Chart 4
1
(Scheme 5) is further manifested by the H NMR spectrum at
-20 °C, which shows three SnCH2 resonances at δ 1.50, 1.56,
and 1.79. At 87 °C only one resonance at δ 1.74 (2J(1H-119Sn)
3
78 Hz, J(1H-1H) 6 Hz) was observed.

4176 Organometallics, Vol. 26, No. 17, 2007
Reeske et al.
Electrospray mass spectra were recorded in the positive mode
on a Thermoquest-Finnigan instrument using CH3CN as the mobile
phase. The samples were introduced as a solution in a mixture of
CH3CN and 1% formic acid (9:1 ratio) (c ) 10-4 mol L-1) via a
syringe pump operating at 0.5 µL/min. The capillary voltage was
4.5 kV, while the cone skimmer voltage was varied between 50
and 250 kV. Identification of the inspected ions was assisted by
comparison of experimental and calculated isotope distribution
patterns. The m/z values reported correspond to those of the most
intense peak in the corresponding isotope pattern.
Crystallography. Intensity data for the colorless crystals were
collected on a Nonius KappaCCD diffractometer with graphite-
monochromated Mo KR (0.71073 Å) radiation at 173(1) K. The
data collection covered almost the whole sphere of reciprocal space
with three (2, 5, 7, 8) and four (1, 3, 4) sets at different k-angles
with 395 (1), 298 (2), 182 (3), 419 (4), 207 (5), 310 (7), and 263
(8) frames via ω-rotation [∆/ω ) 1° (1, 2, 4, 7, 8) and ∆/ω ) 2°
(3, 5)] at two times 10 s (3, 4), 12.5 s (2), and 60 s (4) per frame.
The crystal-to-detector distances were 3.4 cm (2-8) and 4.4 cm
(1). Crystal decays were monitored by repeating the initial frames
at the end of data collection. The data were not corrected for
absorption effects. Analyzing the duplicate reflections, there were
no indications for any decay. The structures were solved by direct
methods (SHELXS9749) and successive difference Fourier synthe-
ses.Refinementappliedfull-matrixleast-squaresmethods(SHELXL9750).
The H atoms were placed in geometrically calculated positions
using a riding model with isotropic temperature factors constrained
at 1.2 for non-methyl and at 1.5 for methyl groups times Ueq of the
carrier C atom. In 7 one C atom is disordered over two positions
with occupancies of 0.5 (C(27), C(27′)). Each solvent molecule
CH2Cl2 in 3 and 4 is anisotropically refined with occupancies of
0.5. Atomic scattering factors for neutral atoms and real and
imaginary dispersion terms were taken from ref 51. The figures
were created by SHELXTL.52
was stirred overnight. The solvent and the iodobenzene were
removed in vacuo (1 × 10-3 Torr). Addition of CH2Cl2 (20 mL),
filtration, and evaporation of the solvent afforded 7.55 g (99% yield)
1
3
of 3 as colorless crystals. H NMR (CDCl3) δ: 1.76 (d, J(1H-
2
1H) ) 7.5 Hz, J(1H-117/119Sn) ) 73.5 Hz, 2 H, Sn-CH2), 2.58
(m, 1 H, CH), 3.30-3.9 (m, 20 H, CH2-O-CH2), 7.30-7.90 (m,
10 H, Ph). 13C{1H} NMR (CDCl3) δ: 20.46 (Sn-CH2-), 37.78
(C15), 69.59-70.42 (C2-C12), 74.34 (C14/C16), 128.52 (3J(13C-
117/119Sn) ) 62.4 Hz, Cm), 129.32 (4J(13C-117/119Sn) ) 13.4 Hz,
Cp), 135.89 (2J(13C-117/119Sn) ) 46.1 Hz, Co), 140.20 (Ci). 119Sn-
{1H} NMR (CH2Cl2, D2O-Cap.) δ: -130.2. Anal. Calcd (%) for
C24H33IO5Sn (647.13): C 44.5, H 5.1. Found: C 44.6, H 5.0. Mp:
102-103 °C.
Synthesis of Bromo(1,4,7,10,13-pentaoxacyclohexadec-15-yl-
methyl)diphenylstannane (3). Bromine (1.3 g, 8.40 mmol) in
dichloromethane (50 mL) was added dropwise to a cooled solution
(-55 °C) of 1 (5.00 g, 8.40 mmol) in dichloromethane (100 mL).
The reaction mixture was allowed to warm to room temperature
over night to give a clear solution. From this solution all volatiles
were removed in vacuo to afford a light yellow solid, which was
recrystallized from ethanol to give colorless crystals (4.9 g, 98%).
3
1H NMR (400.13 MHz, CDCl3, 298 K) δ: 1.64 (d, J(1H-1H)
) 8.0 Hz, 2J(1H-117/119Sn) ) 76.8 Hz, 2 H, Sn-CH2), 2.47-2.70
(m, 1 H, CH), 3.28-3.84 (m, 20 H, CH2-O-CH2), 7.32-7.43
3
4
(m, 6 H, Phm,p), 7.69 (dd, J(1H-1H) ) 7.8 Hz, J(1H-1H) ) 1.8
Hz, H(1H-117/119Sn) ) 60 Hz, 4 H, Pho). 13C{1H} NMR (100.63
3
MHz, CDCl3, 298 K) δ: 18.55 (1J(13C-117Sn) ) 507.3 Hz, 1J(13C-
119Sn) ) 531.0 Hz, Sn-CH2-), 37.28 (C(15)), 69.58-70.39 (C(2)-
C(12)), 74.38 (3J(13C-117/119Sn) ) 70.0 Hz, C(14)/C(16)), 128.59
(3J(13C-117/119Sn) ) 65.0 Hz, Cm), 129.39 (4J(13C-117/119Sn) ) 14.0
Hz, Cp), 135.81 (2J(13C-117/119Sn) ) 47.0 Hz, Co), 140.67 (Ci).
119Sn{1H} NMR (149.21 MHz, CDCl3, 298 K) δ: -96. Anal. Calcd
for C24H33BrO5Sn‚1/2CH2Cl2 (642.60): C 45.8 H 5.3. Found: C
46.0, H 5.2. Mp: 84-86 °C.
Crystallographic data are given in Table 5, and selected bond
distances and angles in Tables 1 and 2 (1-5) and Tables 3 and 4
(3, 4).
Synthesis of Chloro(1,4,7,10,13-pentaoxacyclohexadec-15-
ylmethyl)diphenylstannane (4). AgCl (4.7 g, 32.5 mmol) was
added to a solution of 3 (7.0 g, 10.8 mmol) in CH3CN (150 mL)
and stirred in the dark for 14 days. The resulting AgI and the
nonreacted AgCl were filtered, and the filtrate was evaporated in
vacuo to give a light yellow oil. The oil was dissolved in CH2Cl2/
Et2O (2:1) and cooled to -5 °C for several days. providing 5.9 g
(98%) of pure 3. 1H NMR (CD2Cl2) δ: 1.58 (d, 3J(1H-1H) ) 8.0
Hz, 2J(1H-117/119Sn) ) 40.2 Hz, 2 H, Sn-CH2), 2.59 (m, 1 H, CH),
3.30-3.85 (m, 20 H, CH2-O-CH2), 7.68-7.50 (m, 6 H, Phm,p),
7.64-7.83 (m, 4 H, Pho). 13C{1H} NMR (CD2Cl2) δ: 17.25
(1J(13C-117Sn) ) 548.2 Hz, 1J(13C-119Sn) ) 523.9 Hz, Sn-CH2-
), 37.17 (2J(13C-117/119Sn) ) 23.3 Hz, C15), 69.78-70.45 (C2-
C12), 74.43 (3J(13C-117/119Sn) ) 71.9 Hz, C14/C16), 128.65
(3J(13C-117/119Sn) ) 64.2 Hz, Cm), 129.46 (4J(13C-117/119Sn) ) 13.6
Hz, Cp), 135.84 (2J(13C-117/119Sn) ) 46.7 Hz, Co), 141.09 (1J(13C-
117Sn) ) 636.7 Hz, 1J(13C-119Sn) ) 726.3 Hz, Ci). 119Sn{1H} NMR
(CD2Cl2) δ: -88. 119Sn MAS δ: -73 (∆δ -278.7, η 0.8). Anal.
Calcd for C24H33ClO5Sn‚1/2CH2Cl2 (598.1): C 49.2, H 5.7.
Found: C 49.1, H 5.9. Mp: 76-78 °C.
Synthesis of (1,4,7,10,13-Pentaoxacyclohexadec-15-ylmethyl)-
triphenylstannane (1). 15-Methylene-1,4,7,10,13-pentaoxacyclo-
hexadecan (10 g, 40 mmol) and aibn (115 mg) were added to
Ph3SnH (14.26 g, 40 mmol). The mixture was stirred at 70 °C for
12 h followed by cooling to room temperature, addition of CH2Cl2
(50 mL), and filtration of the solution through Celite. After the
solvent had been removed in vacuum a light yellow oil remained.
The purification of this oil was achieved by column chromatography
with silica gel and CH2Cl2. Elution with ethanol gave 18.6 g (78%)
1
3
2
of 1. H NMR (CDCl3) δ: 1.45 (d, J(1H-1H) ) 7.5 Hz, J(1H-
117/119Sn) ) 58.8 Hz, 2H, Sn-CH2), 2.43 (m, 1 H, CH), 3.28-
3.69 (m, 20 H, CH2-O-CH2), 7.31-7.63 (m, 15 H, Ph). 13C{1H}
NMR (CDCl3) δ: 11.35 (Sn-CH2-), 37.10 (2J(13C-117/119Sn) )
20.1 Hz, C15), 69.47-70.72 (C2-C12), 74.20 (C14/C15), 128.13
(3J(13C-117/119Sn) ) 48.0 Hz, Cm), 128.36 (4J(13C-117/119Sn) ) 11.5
Hz, Cp), 136.86 (2J(13C-117/119Sn) ) 35.5 Hz, Co), 140.39 (1J(13C-
117/119Sn) ) 497.1 Hz, Ci). 119Sn {1H} NMR (CH2Cl2, D2O-Cap.)
δ: -110.2. Anal. Calcd for C30H38O5Sn (597.33): C 60.3; H 6.4.
Found: C 60.3; H 6.4. Mp: 60 °C.
Synthesis of Fluoro(1,4,7,10,13-pentaoxacyclohexadec-15-yl-
methyl)diphenylstannane (5). A solution of 2 (2 g, 3.10 mmol)
in CH2Cl2 (50 mL) was treated with tetrabutylammonium fluoride
(5.7 g, 31 mmol) and stirred for 12 h at room temperature. Washing
with water (3 × 50 mL), drying over Na2SO4, and removing the
solvent led to a colorless solid, which was recrystallized from CH2-
Cl2/n-hexane (1:1) at -5 °C, resulting in 1.0 g (63%) of colorless
crystals. 1H NMR (CDCl3) δ: 1.41 (d, 3J(1H-1H) ) 8.0 Hz, 2J(1H-
117/119Sn) ) 80.3 Hz, 2 H, Sn-CH2), 2.57 (m, 1 H, CH), 3.32-
3.86 (m, 20 H, CH2-O-CH2), 7.32-7.44 (m, 6 H, Sn-Ph Hm,p),
Synthesis of Iodo(1,4,7,10,13-pentaoxacyclohexadec-15-ylm-
ethyl)diphenylstannane (2). Iodine (2.98 g, 11.75 mmol) was
added in small portions under ice cooling to a stirred solution of 1
(7.00 g, 11.75 mmol) in CH2Cl2 (50 mL). The reaction mixture
(48) Kuivila, H. G.; Beumel, O. F. J. Am. Chem. Soc. 1961, 83, 1246.
(49) Sheldrick, G. M. Acta Crystallogr. Sect. A: Found. Crystallogr.
1990, 46, 467.
(50) Sheldrick, G. M. SHELXL97; University of Go¨ttingen, 1997.
(51) International Tables for X-ray Crystallography; Kluwer Academic
Publishers: Dordrecht, 1992; Vol. C.
3
7.56-7.76 (m, J(1H-117/119Sn) ) 60.8 Hz, Sn-Ph Ho). 13C{1H}
NMR (CDCl3) δ: 20.46 (2J(13C-19F) ) 12.6 Hz, Sn-CH2-), 36.58
(C15), 69.62-70.36 (C2-C12), 74.42 (3J(13C-117/119Sn) ) 69.0
(52) Sheldrick, G. M. SHELXTL (Release 5.1, Software Reference
Manual); Bruker AXS, Inc.: Madison, WI, 1997.

Ph(3-n)XnSnCH2-16-crown-5 (X ) F, Cl, Br, I, SCN; n ) 1, 2)
Organometallics, Vol. 26, No. 17, 2007 4177

4178 Organometallics, Vol. 26, No. 17, 2007
Reeske et al.
Hz, C14/C16), 128.53 (3J(13C-117/119Sn) ) 63.2 Hz, Cm), 129.47
(4J(13C-117/119Sn) ) 13.6 Hz, Cp), 135.81 (2J(13C-117/119Sn) ) 45.7
Hz, Co), 140.63 (2J(13C-19F) ) 13.6 Hz, Ci). 19F{1H} NMR
(CDCl3) δ: -189.3 (s, 1J(19F-117Sn) ) 2116.4 Hz, 1J(19F-119Sn)
) 2212.4 Hz, Sn-F). 119Sn{1H} NMR (CH2Cl2, D2O-Cap.) δ:
-106.3 (d, 1J(119Sn-19F) ) 2206.8 Hz. Anal. Calcd (%) for C24H33-
FO5Sn (539.22): C 53.5, H 6.2. Found: C 53.2, H 6.1. Mp: 108-
109 °C.
Complexation Studies. Reaction of 4 with NaBPh4. NaBPh4
(34.9 mg, 1.02 × 10-4 mol) was added to a solution of 3 (56.5
1
mg, 1.02 × 10-4 mol) in CD2Cl2. H NMR (CD2Cl2) δ: 1.79 (d,
3J(1H-1H) ) 8 Hz, 2J(1H-117/119Sn) ) 56 Hz, 2 H, Sn-CH2), 2.50
(m, 1 H, CH), 3.20-3.27 (m, 2 H, CH2-O-CH2), 3.40-3.65 (m,
18 H, CH2-O-CH2), 6.98 (t, 4 H BPh4-), 7.13 (t, 8 H, BPh4-),
7.43 (m, 8 H, BPh4-), 7.56-7.60 (m, 6 H, Phm,p), 7.65-7.75 (m,
4 H, Pho). 13C{1H} NMR (CD2Cl2) δ: 16.58 (1J(13C-117Sn) ) 414.6
Hz, 1J(13C-119Sn) ) 434.7 Hz, Sn-CH2-), 36.92 (2J(13C-117/119
-
Synthesis of Thiocyanato(1,4,7,10,13-pentaoxacyclohexadec-
15-ylmethyl)diphenylstannane (6). AgSCN (1.0 g, 1.55 mmol)
was added to a solution of 2 (0.77 g, 4.64 mmol) in CH3CN (50
mL), and the reaction mixture was stirred in the dark for 3 days
followed by filtration of the AgI formed and the nonreacted AgSCN.
The filtrate was removed in vacuo to give a light yellow oil. The
oil was dissolved in EtOH (30 mL) and cooled to -5 °C for several
days, yielding 0.5 g (98%) of pure 6. 1H NMR (599.83 MHz,
CDCl3) δ: 1.52 (d, 3J(1H-1H) ) 6.0 Hz, 2J(1H-117/119Sn) ) 72.0
Hz, 2 H, Sn-CH2), 2.57 (m, 1 H, CH), 3.25-3.85 (m, 20 H, CH2-
O-CH2), 7.35-7.45 (m, 6 H, Phm,p), 7.55-7.73 (m, 4 H, Pho).
13C{1H} NMR (150.84 MHz, CDCl3) δ: 14.58 (CH2), 36.89-
(2J(13C-117/119Sn) ) 21.1 Hz, C(15)), 70.09-70.54 (C(2)-C(12)),
74.66 (3J(13C-117/119Sn) ) 69.4 Hz, C(14)/C(16)), 129.16 (3J(13C-
117/119Sn) ) 64.9 Hz, Cm), 130.15 (Cp], 136.07 [2J(13C-117/119Sn)
) 46.8 Hz, Co], 138.68 [Ci], 141,01 [NdCdS]. 14N{1H} NMR
(28.91 MHz, CDCl3) δ: -235.6 (ν1/2 ) 65 Hz). 119Sn{1H} NMR
Sn) ) 27.2 Hz, C15), 69.40-71.08 (C2-C12), 78.05 (3J(13C-
117/119Sn) ) 47.3 Hz, C14/C16), 122.20 (BPh4-) 126.05 (BPh4-),
126.66 (3J(13C-117/119Sn) ) 60.4 Hz, Cm), 130.98 (4J(13C-117/119
-
Sn) ) 12.1 Hz, Cp), 135.94 (2J(13C-117/119Sn) ) 47.3 Hz, Co),
136.41 (BPh4-), 139.22 (1J(13C-117Sn) ) 551.5 Hz, J(13C-119
-
1
Sn) ) 576.6 Hz Ci), 164.17 (q, BPh4-). 23Na{1H} NMR (CD2Cl2)
δ: 1.40 (ν1/2 ) 2232 Hz). 119Sn{1H} NMR (CD2Cl2, 298 K) δ: no
signal observed. 119Sn{1H} NMR (CD2Cl2, 238 K) δ: 13.2 (ν1/2
)
207 Hz).
Reaction of 4 with [Ph3P)2N]Cl. [(Ph3P)2N]Cl (116.3 mg, 2.03
× 10-4 mol) was added to a solution of 3 (112.5 mg, 2.03 × 10-4
mol) in CD2Cl2. 119Sn{1H} NMR (CD2Cl2, 298 K) δ: -120.7
(96%). 119Sn{1H} NMR (CD2Cl2, 203 K) δ: -89.2 (65%), -198.6
(35%).
Reaction of 4 with Excess [Ph3P)2N]Cl. [(Ph3P)2N]Cl (161.2
mg, 2.81 × 10-4 mol) was added to a solution of 3 (78.0 mg, 1.40
× 10-4 mol) in CD2Cl2. 119Sn{1H} NMR (CD2Cl2, 298 K) δ:
-144.0 (96%). 119Sn{1H} NMR (CD2Cl2, 203 K) δ: -89.3 (47%),
-198.3 (53%).
1
(149.21 MHz, CD2Cl2) δ: -154.9 (t, J(119Sn-14N) ) 142 Hz).
Anal. Calcd (%) for C25H33NO5SSn (578.31): C 51.9, H 5.8, N
2.4. Found: C 50.9, H 5.7, N 2.5.
Reaction of 4 with Excess Me4NF. Me4NF‚H2O (55.9 mg, 3.38
× 10-4 mol) was added to a solution of 3 (94.0 mg, 1.69 × 10-4
mol) in CD2Cl2. 119Sn{1H} NMR (CD2Cl2, 298 K) δ: -110.6 (d,
1J(119Sn-19F) ) 2223 Hz). 119Sn{1H} NMR (CD2Cl2, 203 K) δ:
Synthesis of Dichloro(1,4,7,10,13-Pentaoxacyclohexadec-15-
ylmethyl)phenylstannane (7). Hydrogen chloride gas (dried over
molecular sieves) was bubbled through (1 h) a cooled solution (-78
°C) of 1 (2 g, 3.36 mmol) in CH2Cl2. All volatiles were removed
under vacuum, and the remaining oil consisting of the triorganotin
chloride 3 and the diorganotin dichloride 7 was warmed to room
temperature. The oil was dissolved in Et2O and kept at -5 °C for
several days, providing, after filtration, 0.5 g (23%) of the
diorganotin dichloride 7 as colorless crystals.
1
-108.0 (d, J(119Sn-19F) ) 2187 Hz).
In Situ Reaction of 4 with NaI. NaI (22.3 mg, 1.49 × 10-4
mol) was added to a solution of 3 (82.7 mg, 1.49 × 10-4 mol) in
CD2Cl2. 119Sn{1H} NMR (CD2Cl2, 298 K) δ: -86.7 (41%, ν1/2
)
454 Hz), -129.4 (59%, ν1/2 ) 794 Hz). 119Sn{1H} NMR (CD2Cl2,
203 K) δ: -88.9 (48%), -129.5 (52%).
1H NMR (CDCl3) δ: 1.77 (d, 3J(1H-1H) ) 6.0 Hz, 2J(1H-117/119
-
In Situ Reaction of 4 with Excess NaI. NaI (539 mg, 3.6 ×
10-4 mol) was added to a solution of 3 (500 mg, 9.0 × 10-4 mol)
in chloroform. The solution was refluxed for 1 h and stirred at room
temperature for 12 h. Filtering of the solution and removing of all
volatiles gave a yellow solid. 1H NMR (CD2Cl2) δ: 2.22 (d, 3J(1H-
Sn) ) 93.4 Hz, 2 H, Sn-CH2), 2.60 (m, 1 H, CH), 3.47-3.95 (m,
20 H, CH2-O-CH2), 7.34-7.45 (m, 3 H, Phm,p), 7.73-7.99 (m, 2
H, Pho). 13C{1H} NMR (CDCl3) δ: 26.40 (1J(13C-117Sn) ) 706.7
Hz, 1J(13C-119Sn) ) 738.8 Hz, Sn-CH2-), 35.65 (2J(13C-117/119
Sn) ) 44.7 Hz C15), 69.69-70.26 (C2-C12), 73.74 (3J(13C-117/119
-
-
2
1H) ) 8.0 Hz, J(1H-117/119Sn) ) 57.5 Hz, 2 H, Sn-CH2), 2.46
Sn) ) 61.2 Hz, C14/C16), 128.64 (3J(13C-117/119Sn) ) 91.4 Hz,
Cm), 130.22 (4J(13C-117/119Sn) ) 18.4 Hz, Cp), 135.33 (2J(13C-
117/119Sn) ) 65.2 Hz, Co), 142.97 (1J(13C-117Sn) ) 929.3 Hz,
1J(13C-119Sn) ) 971.1 Hz, Ci). 119Sn{1H} NMR (CH2Cl2, D2O-
Cap.) δ: -125.1. Anal. Calcd (%) for C18H28Cl2O5Sn (514.03):
C 42.1, H 5.5. Found: C 42.1, H 5.6. Mp: 160-162 °C.
(m, 1 H, CH), 3.02-3.06 (m, 2 H, CH2-O-CH2), 3.36-3.80 (m,
18 H, CH2-O-CH2), 7.30-7.44 (m, 6 H, Phm,p), 7.73-7.94 (m, 4
H, Pho). 13C{1H} NMR (CD2Cl2) δ: 20.75 (1J(13C-117Sn) ) 415.1,
1J(13C-119Sn) ) 434.5, Sn-CH2-), 37.00 (2J(13C-117/119Sn) ) 25.3
Hz, C15), 68.97-70.34 (-CH2-O-), 77.56 (3J(13C-117/119Sn) )
54.4 Hz, C14/C16), 128.51 (3J(13C-117/119Sn) ) 60.4 Hz, Cm),
Synthesis of Diiodo(1,4,7,10,13-pentaoxacyclohexadec-15-yl-
methyl)phenylstannane (8). Iodine (3.72 g, 15.50 mmol) was
added in small portions under ice cooling to a stirred solution of 1
(4.37 g, 7.32 mmol) in CH2Cl2 (50 mL). The reaction mixture was
stirred overnight. The solvent and the iodobenzene were removed
in vacuo (1 × 10-3 Torr). Addition of CH2Cl2 (20 mL) to the
residue and stirring for 5 min, followed by filtration and evaporation
of the solvent afforded 8 (5.0 g, 98%) as yellow crystals. 1H NMR
(CDCl3) δ: 2.16 (d, 3J(1H-1H) ) 7.0 Hz, 2J(1H-117/119Sn) ) 75.6
Hz, 2 H, Sn-CH2), 2.57 (m, 1 H, CH), 3.30-3.9 (m, 20 H, CH2-
O-CH2), 7.30-7.81 (m, 5 H, Ph). 13C{1H} NMR (CDCl3) δ: 29.90
(Sn-CH2-), 38.03 (C15), 69.67-70.38 (C2-C12), 73.32 (C14/
C16), 128.51 (3J(13C-117/119Sn) ) 85.5 Hz, Cm), 130.12 (4J(13C-
117/119Sn) ) 19.4 Hz, (Cp), 134.36 (2J(13C-117/119Sn) ) 62.2 Hz,
Co), 140.84 (Ci). 119Sn{1H} NMR (CH2Cl2, D2O-Cap.) δ: -266.1.
Anal. Calcd (%) for C18H28I2O5Sn (696.93): C 31.0, H 4.1.
Found: C 31.4, H 4.0. Mp: 177-178 °C.
129.50 (4J(13C-117/119Sn) ) 13.6 Hz, Cp), 136.38 (2J(13C-117/119
-
1
Sn) ) 47.6 Hz, Co), 139.32 (1J(13C-117Sn) ) 530.7 Hz, J(13C-
119Sn) ) 554.1 Hz, Ci). 119Sn{1H} NMR (CD2Cl2) δ: -61.
In Situ Reaction of 4 with NaSCN. NaSCN (5 mg, 6.21 ×
10-5 mol) was added to a solution of 4 (34.5 mg, 6.21 × 10-5
1
mol) in C2D2Cl4. H NMR (300 K, C2D2Cl4) δ: 1.75 (s, br, 2 H,
Sn-CH2), 2.59 (s, br, 1 H, CH), 3.00-4.0 (m, br, 20 H, CH2-
O-CH2), 7.25-7.50 (m, 6 H, Phm,p), 7.75-7.25 (m, br, 4 H, Pho).
13C{1H} NMR (300 K, C2D2Cl4) δ: 37.29 (C15), 69.00-72.00 (br,
-CH2-O-), 128.89 (Cm), 129.69 (Cp), 136.33 (2J(13C-117/119Sn)
) 47.6 Hz, Co). 119Sn{1H} NMR (300 K, C2D2Cl4) δ: -89 (ν1/2
) 219 Hz, 43%), -157 (ν1/2 ) 325 Hz, 18%), -229 (ν1/2 ) 219
Hz, 39%).
1H NMR (253 K, C2D2Cl4) δ: 1.50, 1.56, and 1.79 (s, br, 2 H,
Sn-CH2), 2.42 and 2.59 (s, br, 1 H, CH), 2.80 (s, br, 2 H, CH2-
O-CH2), 3.25-3.75 (m, br, 16 H, CH2-O-CH2),7.40-7.45 (m,
6 H, Phm,p), 7.64, 7.71, 7.97 (s, br, 4 H, Pho). 13C{1H} NMR (253

Ph(3-n)XnSnCH2-16-crown-5 (X ) F, Cl, Br, I, SCN; n ) 1, 2)
Organometallics, Vol. 26, No. 17, 2007 4179
K, C2D2Cl4) δ: 14.53, 17.45, 22.55 (SnCH2), 36.98, 37.10, 37.28
(C15), 69.34-71.00 (br, -CH2-O-), 74.72, 78.76 (C14/C16) 128.74,
129.25, 129.49 (Cm), 129.88, 130.17, 130.57 (Cp), 136.07, 136.63
(Co), 140.89, 141.91 (Ci). 119Sn{1H} NMR (253 K, C2D2Cl4) δ:
-93 (ν1/2 ) 50 Hz, 48%), -159 (ν1/2 ) 92 Hz, 14%), -229 (ν1/2
) 107 Hz, 38%).
(s, br, 4 H, Pho). 13C{1H} NMR (300 K, CDCl3) δ: 18.91, 23.30
(SnCH2). 37.19 (2J(13C-117/119Sn) ) 25 Hz, C15), 69.57-70.53
(-CH2-O-), 78.89 (C14/C16), 128.66 (Cm), 129.40 (Cp), 136.78
(Co), 137.70 (Ci), 142.32 (SCN). 119Sn{1H} NMR (300 K, CDCl3)
119
δ: -155 (ν1/2 ) 418 Hz, 62%), -225 (ν1/2 ) 154 Hz, 38%).
-
Sn{1H} NMR (300 K, CDCl3, after 10 days) δ: -225 (ν1/2 ) 154
Hz, 100%).
3
1H NMR (360 K, C2D2Cl4) δ: 1.74 (s, J(1H-1H) ) 6 Hz,
2J(1H-117/119Sn) ) 78, 2 H, Sn-CH2), 2.63 (m, 1 H, CH), 3.32 (s,
br, 2 H, CH2-O-CH2), 3.48-3.77 (m, br, 16 H, CH2-O-
CH2),7.44-7.48 (m, 6 H, Phm,p), 7.84 (s, br, 4 H, Pho). 13C{1H}
NMR (360 K, C2D2Cl4) δ: 37.46 (C15), 70.13-70.70 (-CH2-
O-), 75.96 (C14/C16) 128.88 (3J(13C-117/119Sn) ) 68 Hz, Cm),
129.71 (Cp), 136.29 (2J(13C-117/119Sn) ) 47 Hz, Co). 119Sn{1H}
NMR (313 K, C2D2Cl4) δ: no signal observed.
In Situ Reaction of 4 with AgClO4. AgClO4 (0.236 g, 1.14
mmol) was added to a solution of 2 (0.737 g, 1.14 mmol) in CH3-
CN (20 mL), and the reaction mixture was stirred in the dark for
2 days. After the resulting AgI had been filtered the solvent of the
filtrate was evaporated in vacuo to give a colorless oil. 119Sn{1H}
NMR (CDCl3) δ: -71.1
In Situ Reaction of 4 with 2 equiv of NaSCN. NaSCN (21
mg, 2.61 × 10-4 mol) was added to a solution of 4 (73 mg, 1.31
× 10-4 mol) in C2D2Cl4. 119Sn{1H} NMR (300 K, C2D2Cl4) δ:
-90 (ν1/2 ) 155 Hz, 41%), -157 (ν1/2 ) 260 Hz, 10%), -232
(ν1/2 ) 205 Hz, 48%).
Acknowledgment. The authors thank Dr. D. Heidemann,
Humboldt University Berlin, for recording the 119Sn MAS NMR
spectrum of compound 4. We also acknowledge Mrs. Sylvia
Marzian from Dortmund University for recording the electro-
spray ionization mass spectra. The authors are grateful to one
anonymous reviewer for valuable comments.
In Situ Reaction of 6 with NaCl. NaCl (7 mg, 1.21 × 10-4
mol) was added to a solution of 6 (70 mg, 1.21 × 10-4 mol) in
CDCl3. 119Sn{1H} NMR (300 K, CDCl3) δ: -85 (ν1/2 ) 121 Hz,
25%), -156 (ν1/2 ) 432 Hz, 58%), -229 (ν1/2 ) 243 Hz, 17%).
In Situ Reaction of 6 with NaSCN. NaSCN (10 mg, 1.21 ×
10-4 mol) was added to a solution of 6 (70 mg, 1.21 × 10-4 mol)
Supporting Information Available: ORTEP drawings of the
molecular structures of compounds 2, 3, and 5, the 14N and 119Sn
NMR spectra of compound 6, and the 23Na NMR spectra of NaBPh4
and of 4 + NaBPh4. CIF files for compounds 2-5, 7, and 8. This
materialisavailablefreeofchargeviatheInternetathttp://pubs.acs.org.
1
in CDCl3. H NMR (300 K, CDCl3) δ: 1.56, 1.84 (s, 2 H, Sn-
CH2), 2.55 (m, br, 1 H, CH), 3.86 (s, br, 2 H, CH2-O-CH2), 3.40-
3.75 (m, br, 16 H, CH2-O-CH2),7.36 (m, 6 H, Phm,p), 7.71, 7.98
OM700304P