Organotin compounds Ph2XSnCH2-[19]-crown-6 (X = Ph, F, Cl, Br, I, SCN) and Ph2ISnCH2Sn(I)PhCH 2-[19]-crown-6 as ditopic receptors for potassium salts

Article abstract of DOI:10.1021/om800450k

The syntheses of the organotin-substituted crown ethers Ph ₂XSnCH₂[19]-crown-6 (1, X = Ph; 2, X = Br; 3, X = I; 4, X = Cl; 5, X = F; 6, X = SCN) and Ph₂XSnCH₂Sn(Y)PhCH ₂-[19]-crown-6 (7, X = Y = Ph; 8

Full text of DOI:10.1021/om800450k

Organometallics 2008, 27, 5577–5587
5577
Organotin Compounds Ph2XSnCH2-[19]-crown-6 (X ) Ph, F, Cl,
Br, I, SCN) and Ph2ISnCH2Sn(I)PhCH2-[19]-crown-6 as Ditopic
Receptors for Potassium Salts‡
Alain C. Tagne Kuate, Gregor Reeske, Markus Schu¨rmann, Burkhard Costisella, and
Klaus Jurkschat*
Lehrstuhl fu¨r Anorganische Chemie II, Technische UniVersita¨t Dortmund, D-44221 Dortmund, Germany
ReceiVed May 16, 2008
The syntheses of the organotin-substituted crown ethers Ph2XSnCH2[19]-crown-6 (1, X ) Ph; 2, X )
Br; 3, X ) I; 4, X ) Cl; 5, X ) F; 6, X ) SCN) and Ph2XSnCH2Sn(Y)PhCH2-[19]-crown-6 (7, X ) Y
) Ph; 8, X ) Ph, Y ) I; 9, X ) Y ) I) and of the ditopic complexes 5 · KF, 6 · KSCN, and 9 · KF are
reported. These compounds are characterized by elemental analyses, 1H, 13C, and 119Sn NMR
spectroscopies, electrospray mass spectrometry, and in the cases of 1-4, 8, 9 · H2O, and 9 · KF also by
single-crystal X-ray diffraction studies. The coordination geometry about the tin atoms in compounds 1
and 8 (Sn2) is distorted tetrahedral, whereas it is trigonal bipyramidal for the tin atoms in compounds 2,
3, 4, 8 (Sn1), 9 · H2O, and 9 · KF.
anion binding. This is even more surprising as, to the best of
our knowledge, Reetz’s organoboron-substituted crown ether
(A) was the first representative of this class of compounds that
simultaneously binds cations and anions (here potassium
fluoride, KF).13 Later on, the concept was extended to orga-
noaluminium- (B)14 and organotin- (C-E) substituted crown
ethers,15-17 which were shown to complex lithium chloride,
LiCl, and sodium thiocyanate, NaSCN, respectively, and to
transport the latter through an organic membrane (Chart 1).
Introduction
In recent years so-called ditopic complexation of anions and
cations has become a well-established subdiscipline in supramo-
lecular host-guest chemistry, and both concepts and achieve-
ments in this field have been thoroughly reviewed.1-12 Most
of the ditopic receptors reported to date are purely organic and
employ hydrogen bonding for anion recognition and Lewis-
basic binding sites such as oxygen atoms in crown ethers for
cation recognition. On the other hand, there are only few
examples of ditopic receptors that make use of the Lewis acidity
of organoelement/organometallic moieties or metal cations for
Attempts at ditopically complexing sodium salts of higher
lattice energy such as sodium halides, NaX (X ) F, Cl, I), with
the organotin compounds D and E failed, presumably because
of the monotin sites not being Lewis acidic enough to
compensate for the electrostatic Na+X- attraction. Most re-
cently, however, we have demonstrated the ability of compound
F, which contains a second organotin moiety linked via a
methylene bridge to the first tin atom and that makes possible
chelation of fluoride anion to overcome even the high lattice
energy of sodium fluoride and to solubilize the latter in
acetonitrile.18,19
‡ Dedicated to Professor Rudolph Willem on the occasion of his 60th
birthday.
* Corresponding author. E-mail: klaus.jurkschat@uni-dortmund.de.
(1) (a) Katayev, E. A.; Melfi, P. J.; Sessler J. L. In Modern Supramo-
lecular Chemistry: Stragegies for Macrocyclic Synthesis; Diedrich, F., Stang,
P., Tykwinski, R. R., Eds.; Wiley-VCH: Weinheim, 2008; p 315. (b)
Katsuhiko, A.; Toyoki, K. In Supramolecular Chemistry-Fundamentals
and Applications: The Chemistry of Molecular Recognition-Host Molecules
and Guest Molecules; Iwanami, S., Ed.; Springer-Verlag: Berlin, 2006; p
7.
(2) (a) Lankshear, M. D.; Cowley, A. R.; Beer, P. D. Chem. Commun.
2006, 612. (b) Custelcean, R.; Delmau, L. H.; Moyer, B. A.; Sessler, J. L.;
Cho, W. S.; Gross, D.; Bates, G. W.; Brooks, S. J.; Light, M. E.; Gale,
P. A. Angew. Chem. 2005, 117, 2513; Angew. Chem. Int. Ed. 2005, 44,
2537.
Independent from the compounds shown in Chart 1, there
were also reports on ruthenium,20 rhenium,20 zinc,21 and
uranium22 complexes that selectively recognize potassium
(3) Mahoney, J. M.; Stucker, K. A.; Jiang, H.; Carmichael, I.; Brink-
mann, N. R.; Beatty, A. M.; Noll, B. C.; Smith, B. D. J. Am. Chem. Soc.
2005, 127, 2922.
(4) Itsikson, N. A.; Zyryanov, G. V.; Chupakhin, O. N.; Matern, A. I.
Russ. Chem. ReV. 2005, 74, 747.
(5) Smith, B. D. In Macrocyclic Chemistry: Current Trends and Future
PerspectiVes; Gloe, K., Ed.; Springer: Netherlands, 2005: p 137.
(6) Mahoney, J. M.; Nawaratna, G. U.; Beathy, A. M.; Dugan, P. J.;
Smith, B. D. Inorg. Chem. 2004, 43, 5902.
(13) Reetz, M. T.; Niemeyer, C. M.; Harms, K. Angew. Chem., Int. Ed.
Engl. 1991, 30, 1474.
(14) Reetz, M. T.; Johnson, B. M.; Harms, K. Tetrahedron Lett. 1994,
35 (16), 2525.
(15) Kemmer, M.; Biesemans, M.; Gielen, M.; Martins, J. C.; Gramlich,
V.; Willem, R. Chem.-Eur. J. 2001, 7, 4686.
(16) Reeske, G.; Schu¨rmann, M.; Costisella, B.; Jurkschat, K. Eur.
J. Inorg. Chem. 2005, 2881.
(7) Mahoney, J. M.; Beathy, A. M.; Smith, B. D. Inorg. Chem. 2004,
43, 7617.
(17) Reeske, G.; Schu¨rmann, M.; Costisella, B.; Jurkschat, K. Organo-
metallics 2007, 26, 4170.
(18) Reeske, G.; Bradtmo¨ller, G.; Schu¨rmann, M.; Jurkschat, K. Chem.
Eur. J. 2007, 13, 10239.
(19) Reeske, G.; Schu¨rmann, M.; Jurkschat, K. Dalton Trans. 2008,
3398.
(8) Gale, P. A. Coord. Chem. ReV. 2003, 240, 1.
(9) Webber, P. R. A.; Beer, P. D. Dalton Trans. 2003, 2249.
(10) Beer, P. D.; Gale, P. A. Angew. Chem. 2001, 113, 502; Angew.
Chem. Int. Ed. 2001, 40, 486.
(11) Mahoney, J. M.; Beatty, A. M.; Smith, B. D. J. Am. Chem. Soc.
2001, 123, 5847.
(12) Kirkovits, G. J.; Shriver, J. A.; Gale, P. A.; Sessler, J. L. J. Inclusion
Phenom. Macrocyclic Chem. 2001, 41, 69.
(20) Beer, P. D.; Dent, S. W. Chem. Commun. 1998, 825.
(21) Kim, Y-H.; Hong, J.-I. Chem. Commun. 2002, 512.
(22) Rudkevich, D. M.; Mercer-Chalmers, J. D.; Verboom, W.; Ungaro,
R.; De Jong, F.; Reinhoudt, D. N. J. Am. Chem. Soc. 1995, 117, 6124.
10.1021/om800450k CCC: $40.75
2008 American Chemical Society
Publication on Web 10/08/2008

5578 Organometallics, Vol. 27, No. 21, 2008
Tagne Kuate et al.
Chart 1
Table 1. Selected Bond Distances (Å) for Compounds 1-4
Chart 2
1
2
3
4
X ) C(13) X ) Br(1)
X ) I(1)
X ) Cl(1)
Sn(1)-C(1)
Sn(41)-C(41) 2.147 (2)
Sn(1)-C(7) 2.140 (2)
Sn(41)-C(47) 2.131 (2)
Sn(1)-C(21) 2.143 (2)
Sn(41)-C(53) 2.157 (2)
Sn(1)-X 2.149 (2)
2.145 (2)
2.124 (3)
2.135 (3)
2.115 (3)
2.138 (4)
2.131 (4)
2.128 (5)
2.137 (4)
2.123 (4)
2.111 (4)
2.5846 (4) 2.7896 (4) 2.4323 (11)
2.9820 (13) 2.606 (2) 2.610 (2) 2.606 (2)
Sn(41)-C(61) 2.151 (2)
Sn(1)-O1
Sn(41)-O(41) 2.9963 (14)
dihydrogen phosphate, sodium dihydrogen phosphate, sodium
cyanide, or cesium chloride.
The molecular structure of compound 1 is shown in Figure
1, and selected bond distances and bonds angles are listed in
Tables 1 and 2.
The unit cell contains two independent molecules of 1 with
similar geometric parameters. The tin atoms Sn(1)/Sn(41) adopt
monocapped tetrahedral configurations with the O(1)/O(41)
atoms being the capping ones. They approach the Sn(1) and
The organotin compounds depicted in Chart 1 contain
crown-5 moieties that are specific for sodium cation. In
continuation of our studies mentioned above we report here the
synthesis, molecular structures, and complexation properties in
polar as well as in nonpolar solvents of the corresponding
organotin compounds of types G and H that contain crown-6
moieties being specific for potassium cation (Chart 2). We
demonstrate that both the fluorine-substituted representative of
G-type compounds and the bis(organoiodostannyl)methane-
substituted crown ether of type H are capable of ditopically
complexing potassium fluoride to the extent that the corre-
sponding complexes could be isolated and characterized.
Results and Discussion
Synthesis Aspects and Molecular Structures in the
Solid State. The reaction of 18-methylene-1,4,7,10,13,16-
hexaoxacyclononadecane23 with triphenyltin hydride provided
the organotin-substituted crown ether 1 as a colorless oil that
solidified after it had been kept for some days at room
temperature (eq 1).
Figure 1. Molecular structure of 1 showing 30% probability
displacement ellipsoids and the crystallographic numbering
scheme.
(23) Tomoi, M.; Abe, O.; Ikeda, M.; Kihara, K.; Kakiuchi, H. Tetra-
hedron Lett. 1978, 3031.

Organotin Compounds Ph2XSnCH2-[19]-crown-6
Organometallics, Vol. 27, No. 21, 2008 5579
Table 2. Selected Bonds Angles (deg) for Compounds 1-4
Scheme 1
2
3
4
1
X ) Br(1) X ) I(1) X ) Cl(1)
C(1)-Sn(1)-C(7)
C(1)-Sn(1)-C(21)
C(7)-Sn(1)-C(21)
C(1)-Sn(1)-C(13)
C(7)-Sn(1)-C(13)
109.47(8) 110.5(1)
117.26(8) 119.5(1)
117.14(9) 122.7(1)
105.93(8)
110.4(1)
121.8(1)
120.1(2)
110.4(1)
124.0(2)
118.5(2)
102.44(8)
C(13)-Sn(1)-C(21) 102.53(8)
C(47)-Sn(41)-C(61) 118.33(8)
C(47)-Sn(41)-C(41) 111.24(8)
C(41)-Sn(41)-C(61) 109.70(8)
C(41)-Sn(41)-C(53) 103.36(8)
C(47)-Sn(41)-C(53) 104.21(8)
C(53)-Sn(41)-C(61) 108.77(8)
C(1)-Sn(1)-O(1)
84.14(8)
87.10(8)
72.77(9)
87.69(22) 86.9(1)
83.01(11) 83.9(1)
72.56(13) 73.3(11)
C(7)-Sn(1)-O(1)
C(21)-Sn(1)-O(1)
O(1)-Sn(1)-X
169.69(4) 169.37(6) 170.66(6)
O(1)-Sn(1)-C(13)
170.03(6)
O(41)-Sn(1)-C(53) 168.80(6)
C(1)-Sn(1)-X
99.80(7) 100.61(10) 99.48(11)
100.26(7) 100.03(10) 100.14(10)
97.08(8)
113.9(2)
C(7)-Sn(1)-X
C(21)-Sn(1)-X
97.40(12) 97.43(11)
111.9(3) 113.7(2)
C(22)-C(21)-Sn(1) 118.5(2)
C(62)-C(61)-Sn(41) 114.6(2)
Sn(41) atoms via the tetrahedral faces defined by C(1), C(7),
C(21) and C(41), C(47), C(61), respectively, at Sn(1) · · · O(1)
and Sn(41) · · · O(41) distances of 2.9820(13) and 2.9963(14) Å,
respectively. These distances are shorter than the sum of the
van der Waals radii24 of tin (2.20 Å) and oxygen (1.50 Å) and,
notably, also shorter than the corresponding distance found in
the closely related tetraorganotin compound Ph3SnCH2-[16]-
crown-5 (3.206(1) Å).17 This difference of approximately 0.2
Å sheds some light on the true nature of the intramolecular
Sn · · · O interactions in tetraorganotin compounds such as 1 and
Ph3SnCH2-[16]-crown-5. Both compounds have exactly the
same substituent pattern at the tin atom, suggesting identical
Lewis acidity as well as the same Lewis basicity of the crown
ether oxygens O(1) and O(41). Consequently, the different
Sn · · · O distances are the result of crystal-packing effects rather
than of Lewis acid-Lewis base attraction. The Sn(1) and Sn(41)
atoms lie 0.504(1) and 0.573(1) Å out of the corresponding plane
in the direction of C(13) and C(53), respectively.
Treatment of 1 with 1 molar equiv of bromine and iodine
gave the corresponding triorganotin bromide 2 and the triorga-
notin iodide 3, respectively, in almost quantitative yield.
Reaction of the triorganotin iodide 3 with an excess of AgCl in
acetonitrile over a period of 14 days provided the triorganotin
chloride 4. In a similar manner, compound 3 was converted by
reaction with NaF and AgSCN into the corresponding triorga-
notin fluoride 5 and triorganotin thiocyanate 6, respectively
(Scheme 1).
Figure 2. Molecular structure of 4 showing 30% probability
displacement ellipsoids and the crystallographic numbering scheme.
tions (geometrical goodness ∆∑(θ)25 55.6° (2), 54.3° (3), 55.8°
(4)) with C(1), C(7), and C(21) occupying the equatorial and
O(1) and the corresponding halogen atoms iodine, bromine, and
chlorine, respectively, occupying the axial positions. The Sn(1)
atom is displaced by 0.332(2) (2), 0.345(2) (3), and 0.330(2)
(4) Å from the trigonal plane in the direction of X(1). The
Sn(1)-O(1) distances are rather similar and fall between
2.606(2) (2, 4) and 2.610(2) Å (3). They are slightly longer
than those measured for the corresponding triorganotin halides
Ph2XSnCH2-[16]-crown-517 (X ) I, 2.554(2) Å; X ) Cl,
2.571(1) Å) and comparable with other related26-28 five-
coordinate tin compounds having Sn-O chelation. As result of
the intramolecular O(1)fSn(1) coordination, the Sn(1)-I(1),
Sn(1)-Br(1), and Sn(1)-Cl(1) distances of 2.7896(4), 2.5846(4),
and 2.4323 (11) Å are longer than the corresponding distances
in tetracoordinated triorganotin halides29 and exceed the sums
of the covalent radii24 of the respective atoms by 0.06 (3) and
0.04 (2, 4) Å, respectively.
The triorganotin halides 2-4 are colorless crystalline solids,
whereas the triorganotin fluoride 5 is an amorphous solid and
the thiocyanate 6 is a viscous oil. They are all well soluble in
common organic solvents such as CHCl3, CHCl2, toluene, and
thf. The molecular structures of compounds 2-4 are rather
similar, and only that of the triorganotin chloride 4 is illustrated
in Figure 2; those of the triorganotin bromide and iodide are
given in the Supporting Information (Figures S1, S2). Selected
bond distances and bonds angles for 2-4 are listed in Tables 1
and 2.
(25) Kolb, U.; Dra¨ger, M.; Jousseaume, B. Organometallics 1991, 10,
2737.
(26) Jambor, R.; Dostal, L.; Ruzicka, A.; Cisarova, I.; Brus, J.; Holcapek,
M.; Holecek, J. Organometallics 2002, 21, 3996.
(27) Kayser, F.; Biesemans, M.; Delmotte, A.; Verbruggen, I.; Gielen,
M.; Willem, R.; Tiekink, E. R. T. Organometallics 1994, 13, 4026.
(28) Munguia, T.; Lopez-Cardoso, M.; Cervantes-Lee, F.; Pannel, K. H.
Inorg. Chem. 2007, 46, 1305.
(29) (a) Bokii, N. G.; Struchkov,Yu, T.; Prok’iev, A. K. J. Struct. Chem.
(Eng. Transl.) 1972, 13, 619. (b) Preut, H.; Huber, F. Acta Crystallogr.
Sect. B 1979, 35, 744. (c) Reuter, H.; Puff, H. J. Organomet. Chem. 1989,
379, 223.
The tin atoms in the triorganotin halides 2-4 are pentaco-
ordinated and exhibit distorted trigonal-bipyramidal configura-
(24) Bondi, A. J. Phys. Chem. 1964, 68, 441.

5580 Organometallics, Vol. 27, No. 21, 2008
Tagne Kuate et al.
Scheme 2
Figure 4. Molecular structure of 9 · H2O showing 30% probability
displacement ellipsoids and the crystallographic numbering scheme.
Table 3. Selected Bond Distances (Å) for Compounds 8, 9 · H2O, and
9 · KF
Figure 3. Molecular structure of 8 showing 30% probability
displacement ellipsoids and the crystallographic numbering scheme.
8
9 · H2O
9 · KF
Sn(1)-C(1)
Sn(1)-C(7)
Sn(1)-C(21)
Sn(1)-I(1)
Sn(1)-O(1)
Sn(1)-F(1)
Sn(2)-C(7)
Sn(2)-C(41)
Sn(2)-C(47)
Sn(2)-C(53)
Sn(2)-I(2)
2.140(3)
2.134(3)
2.132(3)
2.8210(4)
2.465(2)
2.156(5)
2.119(4)
2.129(4)
2.8019(6)
2.644(3)
2.151(6)
2.115(5)
2.154(5)
2.9581(7)
Reaction in thf of the triorganotin iodide 3 with triphenylstan-
nylmethylmagnesium bromide30 provided the bis(organostannyl)
methane-substituted crown ether 7 as a colorless oil. Its treatment
with 1 and 2 molar equiv of iodine gave the mono- and diiodine-
substituted compounds 8 and 9, respectively, as slightly yellow,
sharp-melting crystalline materials (Scheme 2).
Single crystals were grown from ethanol at -15 °C (8) or
by slow evaporation (9). For compound 9 single crystals of its
aqua complex, hereafter referred to as 9 · H2O, were obtained.
The molecular structures of 8 and 9 · H2O are shown in
Figures 3 and 4, respectively, and selected geometric parameters
are collected in Tables 3 and 4.
Like for the triorganotin iodide 3, the Sn(1) atom in
compound 8 is pentacoordinated and exhibits a distorted
trigonal-bipyramidal configuration (geometrical goodness
∆∑(θ)25 66.0°) with C(1), C(7), and C(21) occupying the
equatorial and O(1) and I(1) the axial positions, the Sn(1)-O(1)
distance of 2.465(2) Å being shorter and the Sn(1)-I(1) distance
of 2.8210(4) Å being longer than the corresponding distances
in compound 3. The Sn(1) atom is displaced by 0.255(2) Å in
the direction of I(1) from the trigonal plane defined by C(1),
2.198(3)
2.116(5)
2.144(5)
2.137(6)
2.134(3)
2.148(3)
2.148(3)
2.156(3)
2.128(4)
2.135(5)
2.205(5)
2.8442(5)
2.516(3)
2.8706(6)
2.266(3)
Sn(2)-F(1)
Sn(2)-O(1W)
C(7), and C(21). The configuration at Sn(2) is distorted
tetrahedralwithanglesvaryingbetween106.08(12)°(C41-Sn2-C47)
and 115.86(12)° (C7-Sn2-C41).
Both of the tin atoms in 9 · H2O are pentacoordinated and
show a distorted trigonal-bipyramidal configuration (geometrical
goodness ∆∑(θ)25 60.2° (Sn1), 64.2°(Sn2)) with the carbon
atoms C(1), C(7), C(21) (at Sn1), and C(7), C(41), C(47) (at
Sn2) occupying the equatorial and O(1), I((1) (at Sn1) and
O(1W), I(2) (at Sn2) occupying the axial positions. The Sn(1)
atom is displaced by 0.292(3) Å in the direction of I(1) and the
Sn(2) atom is displaced by 0.265(3) Å in the direction of I(2)
from the planes defined by the corresponding carbon atoms.
(30) Seyferth, D.; Andrews, S. B. J. Organomet. Chem. 1971, 30, 151.

Organotin Compounds Ph2XSnCH2-[19]-crown-6
Organometallics, Vol. 27, No. 21, 2008 5581
Table 4. Selected Bond Angles (deg) for Compounds 8, 9 · H2O, and
9 · KF
OfSn1 coordination, while the latter is rather high-field shifted
in comparison with the chemical shift δ -55 of Sn2 and
indicates that the intermolecular O(W)fSn2 interaction is not
preserved in solution. Similarly to the related aqua complex
[Ph2ClSn(CH2)2]-15-benzocrown-5 · H2O,16 in solution com-
pound 9 · H2O might be in fast equilibrium with 9 + H2O, with
the population of the latter dominating at ambient temperature.
However, this was not investigated in more detail. Moreover,
the 1H NMR spectra (400.13 MHz) of compounds 8 and 9 · H2O
show, as a result of their diastereotopism, AB- and ABX-type
resonances for the SnCH2Sn [8: δ 1.30/1.42, 2J(1H-1H) 12 Hz;
9: δ 1.73/1.93, 2J(1H-1H) 12 Hz, 2J(1H-119/117Sn) 67 Hz] and
SnCH2CH [8: δ 0.90/1.40, 2J(1H-1H) 12 Hz, 3J(1H-1H) 7 Hz;
9 · H2O: δ 1.12/1.49, 2J(1H-1H) 12 Hz, 3J(1H-1H) 7 Hz]
protons, respectively, which indicate the Sn(1) atoms (for
numbering see Chart 3) to be configurationally stable on the
1H NMR time scale. This enhanced configurational stability is
the result of intramolecular OfSn coordination and resembles
the NfSn-induced enhanced configurational stability of the tin
atom in (2-Me2NCH2C6H4)MePhSnBr.33
8
9 · H2O
X ) I(2)
9 · KF
X ) I(2)
X ) I(2)
C(1)-Sn(1)-C(7)
C(1)-Sn(1)-C(21)
C(7)-Sn(1)-C(21)
C(1)-Sn(1)-I(1)
C(7)-Sn(1)-I(1)
C(21)-Sn(1)-I(1)
O(1)-Sn(1)-I(1)
Sn(1)-C(7)-Sn(2)
C(7)-Sn(2)-C(41)
C(7)-Sn(2)-C(47)
C(7)-Sn(2)-X
C(41)-Sn(2)-C(47)
C(41)-Sn(2)-X
C(47)-Sn(2)-X
O(1W)-Sn(2)-I(2)
F(1)-Sn(1)-I(1)
F(1)-Sn(2)-I(2)
Sn(1)-F(1)-Sn(2)
113.4(1)
116.3(1)
126.1(1)
98.37(9)
97.08(8)
95.33(9)
168.71(5)
118.6(1)
115.9(1)
110.5(1)
110.4(1)
106.1(1)
112.0(2)
115.5(2)
126.8(2)
102.4(1)
98.9(1)
117.8(2)
117.7(2)
122.5(2)
95.3(2)
92.6(2)
96.2(2)
93.0(1)
165.60(8)
117.6(2)
122.5(2)
120.4(2)
95.6(1)
112.6(2)
98.6(1)
97.1(1)
105.8(2)
115.2(2)
123.3(2)
95.0(1)
117.6(2)
97.5(2)
97.4(2)
176.31(7)
171.12(7)
172.10(8)
98.2(1)
The intramolecular Sn(1)-O(1) distance of 2.644(3) Å is longer
than those in compounds 2-4 and Ph2ISnCH2Sn(I)PhCH2-[16]-
crown-5 · H2O (2.555(2) Å).18 The Sn(2)-O(1W) distance
involving the water molecule being sandwich-like trapped
between Sn(2) and the crown ether-oxygen atoms O(2) and O(3)
amounts to 2.516(3) Å. This distance is slightly longer than
those of 2.440(3) and 2.469(4) Å found in the aqua complexes
Ph2ISnCH2Sn(I)PhCH2-[16]-crown-5 · H2O18 and[Ph2ClSn(CH2)2]-
15-benzocrown-5 · H2O,16 respectively. As in these compounds,
in the aqua complex 9 · H2O the complexation of the water
moleculeissupportedbytwohydrogenbridgeswithO(1W) · · · O(2)
and O(1W) · · · O(3) distances of 2.877(5) and 2.823(4) Å,
respectively. Like for the triorganotin iodide 3, the Sn(1)-I(1)
and Sn(2)-I(2) distances of 2.8019(6) and 2.8442(5) Å,
respectively, exceed the sum of the covalent radii of tin (1.40
Å) and iodine (1.33 Å).
Structures in Solution. The structures in solution of com-
pounds 1-9 are similar to those of the analogous organostannyl-
substituted [16]-crown-5 derivatives.17 Thus, as expected, the
tin atoms in the tetraorganostannanes 1 and 7 and the Sn(2)
atom in compound 8 are essentially tetracoordinated, as
evidenced by 119Sn NMR chemical shifts ranging between δ
-105 (1) and -55 (7), being close to δ -92 and -60 reported
for Ph3SnMe31 and Ph2SnMe2,32 respectively. On the other hand,
the low-frequency 119Sn NMR chemical shifts in CDCl3 of δ
-93 (2), -126 (3), -83 (4), -104 [1J(119Sn-19F) 2200 Hz]
(5), -154 [1J(119Sn-14N) ) 256 Hz] (6), -85 (Sn1 in 8), and
-79 (Sn1 in 9 · H2O) indicate for compounds 2-6, 8, and
9 · H2O that the intramolecular OfSn interactions are retained,
with a more detailed reasoning for this statement being given
in ref 17 by comparison with the 119Sn chemical shifts of
tetracoordinated organotin compounds, having comparable sub-
stituent patterns at the tin atoms but lacking any intra- or
intermolecular coordination. As a representative example of the
monotin compounds 2-6, the 119Sn MAS NMR spectrum of
the triorganotin iodide 3 was recorded. It shows a chemical shift
of δ -128, which is close to the 119Sn NMR chemical shift (δ
-126) found in solution. The 119Sn MAS NMR spectrum of
compound 9 · H2O shows resonances at δ -67 (Sn1) and -171
(Sn2). The former is close to the chemical shift of δ -79 in
solution and confirms unambiguously the persistence of the
Chart 3
In analogy with Ph2XSnCH2-[16]-crown-517 (X ) F, Cl, Br,
I) and in contrast to their nonsymmetric structure in the solid
state, compounds 2-6 exhibit, at ambient temperature and on
the 13C NMR time scale, symmetric structures in solution, as
was evidenced by the 13C spectra showing for each compound
seven resonances for the crown ether carbon atoms (C18, C19/
C17, C2/C15, C3/C14, C5/C12, C6/C11, and C8/C9).
The electrospray ionization mass spectra, hereafter referred
to as ESI-MS, in the positive mode of compounds 2-6 are
characterized by the observation of a mass cluster centered at
m/z 565.2 that is assigned to (Ph2SnCH2-[19]-crown-6)+. The
ESI-MS (positive mode) of compound 9 showed mass clusters
centeredatm/z901.0and805.1thatareassignedto{Ph2ISnCH2Sn-
PhCH2-[19]-crown-6}+ and {Ph2(CH3O)SnCH2SnPhCH2-[19]-
crown-6}+.
Complexation Studies. The complexation behavior of the
monotin-substituted crown ether derivatives 2-6 toward potas-
sium salts is similar to that of the triorganotin derivatives
Ph2XSnCH2-[16]-crown-517 (X ) F, Cl, Br, I, NCS) toward
sodium salts. Thus, the 119Sn spectra at room temperature of
solutions of the triorganotin thiocyanate 6 in CD3CN/D2O (4:
1) and CDCl3 to each of which had been added 1 molar equiv
of KSCN showed single resonances at δ -232 (ν1/2 ) 426 Hz)
and -240 (ν1/2 ) 162 Hz), respectively. These signals are
assigned to the ditopic complex [6 · KSCN] (Scheme 3), with
the chemical shifts being close to that reported for the related
complex {Ph2(NCS)SnCH2-[16]-crown-5 · NaSCN} (δ -225, in
CDCl3).17
The formation of the complex [6 · KSCN] in CD3CN/D2O
(4:1) gets further support from (i) the 13C NMR, showing high-
frequency chemical shifts of 2.5, 5.3, and 0.3 ppm of the C(ipso),
C20, and C17/C19 resonances, respectively, and (ii) the H
NMR of the crown ether protons, showing high-frequency shifts
of 0.1 ppm.
1
(31) Davies, A. G.; Harrison, P. G.; Kennedy, J. D.; Mitchell, T. N.;
Puddephat, R. J.; McFarlan, W. J. Chem. Soc. A 1969, 1136.
(32) Hunter, B. K.; Reeves, L. W. Can. J. Chem. 1968, 46, 1399.
(33) van Koten, G.; Noltes, J. G. J. Am. Chem. Soc. 1976, 98, 5393.

5582 Organometallics, Vol. 27, No. 21, 2008
Tagne Kuate et al.
Scheme 3
Scheme 4
The 119Sn NMR spectrum of a solution in CDCl3 of the
triorganotin fluoride 5 to which had been added 1 molar equiv
of tetrabutylammonium fluoride trihydrate, n-Bu4NF · 3H2O,
showed a doublet resonance at δ -106 [1J(119Sn-19F) 2084
The electrospray ionization mass spectrum of the authentic
solution (6 + KSCN in CD3CN/D2O (4:1)) displayed in the
positive mode mass clusters centered at m/z 662.2 and 565.3,
which are assigned to [Ph2(SCN)SnCH2-19-crown-6 · K]+ and
[Ph2SnCH2-19-crown-6}]+. In the negative mode a mass cluster
centered at m/z 682.3 was observed, which is assigned with
caution to [Ph2(SCN)Sn-CH2-19-crown-6 · SCN]-. The calcu-
lated value for the latter is, however, m/z 681.1.
Finally, analytically pure [6 · KSCN] was obtained as a
colorless oil by reaction in dichloromethane/water of the
triorganotin chloride 4 with excess potassium thiocyanate,
KSCN (Scheme 3).
Hz, integral 27] and
a triplet resonance at δ -267
[1J(119Sn-19F) 1860 Hz, integral 73], indicating an equilibrium
between compound 5 and its triorganodifluorostannate complex
[5 · F]-n-Bu4N+. In the latter, fluoride anion successfully
competes with the crown ether oxygen atom for coordination
at the tin atom. Most importantly, the reaction of the triorganotin
fluoride 5 with potassium fluoride, KF, provided the corre-
sponding ditopic complex 5 · KF as a colorless, crystalline,
sharp-melting material (eq 2).
From the investigations on the complexation behavior of
Ph2XSnCH2-[16]-crown-5 (X ) Cl, SCN)17 toward NaSCN and
NaCl, respectively, we know that redistribution reactions take
place involving the ditopic complex Na{Ph2(NCS)2SnCH2-[16]-
crown-5}. A similar behavior holds for [Ph2(SCN)SnCH2-19-
crown-6] toward KCl, with K{Ph2(SCN)2SnCH2-[19]-crown-
6} being involved in the equilibrium. Details are given in the
Supporting Information.
Its 119Sn and 19F NMR spectra show a triplet resonance at δ
-277 [1J(119Sn-19F) 1910 Hz] and a singlet resonance at δ
-157.7 [1J(19F-119Sn) 1912 Hz], respectively, and indicate the
complex to be kinetically inert on the corresponding NMR time
scales. That the potassium cation is indeed coordinated by the
crown ether moiety follows from the 1H and 13C NMR spectra,
which are different as compared to those of the triorganotin
fluoride 5.
Reaction of the bis(organostannyl)methane-substituted crown
ether 9 in methanol with potassium fluoride, KF, provided the
corresponding complex 9 · KF as a single crystalline material
(eq 3).
The 119Sn NMR spectra in CD3CN/D2O solutions of the
triorganotin halides 2, 3, and 4 to which had been added molar
equivalents of potassium bromide, KBr, potassium iodide, KI,
and potassium chloride, KCl, respectively, showed single
resonances at δ -105, -124, and -122 that are close to the
chemical shifts of the parent compounds (2, δ -101; 3, δ -132;
4, δ -91). Together with the 1H and 13C NMR spectra showing
little but unambiguous differences especially of the crown ether
resonances between salt-free and salt-containing solutions, these
results indicate an equilibrium between A and B, and/or C, as
shown in Scheme 4.
The position of this equilibrium depends on the identity of
the halogen X and the concentration of the salt KX (X ) Br, I,
Cl) and reflects the interplay between the strengths of OfSn,
OfK+, Sn-X, and K-X bonds, the hydration energies of K+
and X-, and the donor strength of X- toward the tin atom. Thus,
for X ) I- formation of C seems to be rather unlikely. Indeed,
it appears that the strongest shift of the equilibrium shown in
Scheme 4 toward B and/or C is observed in the case for X )
Br and Cl, respectively. Thus, the 119Sn NMR spectra of
solutions in CD3CN/D2O (7:1) of the organotin bromide 2 and
organotin chloride 4 to which had been added 3 molar equiv of
KBr and 2 molar equiv of KCl, respectively, showed chemical
shifts at δ -125 and -130.
The molecular structure of 9 · KF is shown in Figure 5, and
selected bond distances and bond angles are given in Tables 3
and 4, respectively.
Complex 9 · KF is composed of a dinuclear organotin and a
crown ether moiety that are linked by a methylene group (C21).
Both tin atoms are pentacoordinated and each shows a distorted
trigonal-bipyramidal configuration (geometrical goodness
∆∑(ϑ)25 73.9° (Sn1), 66.2° (Sn2)) with the carbon atoms C(1),

Organotin Compounds Ph2XSnCH2-[19]-crown-6
Organometallics, Vol. 27, No. 21, 2008 5583
longest among the intramolecularly coordinated triorganotin
iodides [(Ph2ISn)2CH2 · F]-[Et4N]+,34 {Ph2ISnCH2Sn(I)PhCH2-
[16]-crown-5} · H2O,18 {Ph2ISnCH2Sn(I)PhCH2-[16]-crown-
5} · NaF · CH3OH,19 3, 8, and 9 · H2O. The origin for this
additional lengthening is very likely the intermolecular
electrostatic I(1A) · · · K(1) attraction, giving rise to a distance
of 3.8294(15) Å, which is only 0.2964 Å longer than the
corresponding distance in crystalline potassium iodide, KI,37
and which compensates part of the charge separation. As a
result of this I(1A) · · · K(1) attraction, compound 9 · KF forms
a polymeric chain in the crystal lattice.
The structure of the crown ether moiety is characterized by
the potassium cation being coordinated by the six crown ether
oxygen atoms at K-O distances ranging between 2.718(4)
(K1-O5) and 2.894(4) Å (K1-O6), which is comparable to
the K-O distances of 2.722(14) and 2.913(15) Å as reported
for the complex formed by a rhenium(I) bipyridine-substituted
crown ether and KCl.38 In addition to the K-O and K · · · I
interactions, there are K(1) · · · C(17b) and K(1) · · · C(25) dis-
tances of 3.498(6) and 3.506(7) Å, respectively, which are
shorter than the sum of the van der Waals radii24 of potassium
and carbon. The potassium cation is placed 0.349(2) Å above
the least plane defined by the six oxygen atoms O(1)-O(6), in
the direction of I(A).
Figure 5. Molecular structure of 9 · KF showing 30% probability
displacement ellipsoids and the crystallographic numbering scheme.
The ditopic complex 9 · KF is preserved in solution and
exhibits a similar behavior to the corresponding complex
{Ph2ISnCH2Sn(I)PhCH2-[16]-crown-5} · NaF.18,19 On the 19F
and 119Sn NMR time scales 9 · KF is kinetically labile at ambient
temperature and kinetically inert at low temperature. These
statements are substantiated by the following experimental facts:
C(7), C(21) (at Sn1) and C(7), C(41), C(47) (at Sn2) occupying
the equatorial and F(1), I(1) (at Sn1) and F(1), I(2) (at Sn2)
occupying the axial positions. The Sn(1) atom is displaced by
0.175(4) Å in the direction of I(1) and the Sn(2) atom is
displaced by 0.246(3) Å in the direction of I(2) from the planes
defined by the corresponding carbon atoms. These data indicate
the configurations of the Sn(1) and Sn(2) atoms in 9 · KF to be
similar to the tin atoms in [(Ph2ISn)2CH2 · F]-[Et4N]+ (∆∑(ϑ)25
72.3°, 69.1°) but somewhat less distorted than those of the tin
atoms in the related ditopic complex {Ph2ISnCH2Sn(I)PhCH2-
[16]-crown-5} · NaF · CH3OH (∆∑(ϑ)25 70.2°, 58.4°).19 As in
the latter compound (∆(Sn-F) 0.128 Å), the Sn(1)-F(1)-Sn(2)
bridge in 9 · KF is unsymmetric (∆(Sn-F) 0.068 Å), whereas
it is almost symmetric in [(Ph2ISn)2CH2 · F]-[Et4N]+ (∆(Sn-F)
0.017 Å).34 The origins for these differences are likely the high
ionic character of the Sn-F bond35 and the CH3O-H · · · F
bridge in {Ph2ISnCH2Sn(I)PhCH2-[16]-crown-5} · NaF · CH3OH.
In complex 9 · KF, like for the sodium fluoride complex
mentioned above,19 the short Sn(1)-F(1) distance (2.198(2) Å)
is associated with the long Sn(1)-I(1) distance (2.9581(7) Å),
whereas the long Sn(2)-F(1) distance (2.266(3) Å) is associated
with the short Sn(2)-I(2) distance (2.8706(6) Å). This is in
line with the usual trend being observed for triorganostannates
that contain a C3SnXY substituent pattern and that exhibit a
combination of short Sn-X/long Sn-Y bonds, or vice
versa.36Further similarities between the structures of 9 · KF
and {Ph2ISnCH2Sn(I)PhCH2-[16]-crown-5} · NaF · CH3OH19
aretheintramolecularF(1) · · · H(6A),F(1) · · · H(8A),F(1) · · · H(14A),
and F(1) · · · H(22A) distances of 2.504, 2.524, 2.363, and
2.558 Å, respectively, being shorter than the sum of the van
der Waals radii24 of fluorine (1.50-1.60 Å) and hydrogen
(1.20-1.45 Å) (see Figure S3 in the Supporting Information).
The Sn(1)-I(1) distance in 9 · KF of 2.9581(7) Å is the
1
(i) In contrast to compound 9 · H2O, the H NMR spectrum
(400.13 MHz, CDCl3) of complex 9 · KF displays a broad singlet
resonance for the SnCH2Sn protons at δ 1.41 (2J(1H-117/119Sn)
76.5 Hz) and a broad doublet resonance for the SnCH2CH
2
protons at δ 1.05 (2J(1H-1H) 6 Hz, J(1H-117/119Sn) 69 Hz).
The data indicate loss of diastereotopism of the methylene
protons associated with decreased configurational stability of
the tin atom. (ii) The 19F NMR spectrum (282.40 MHz, CDCl3)
shows a broad singlet at δ -105.0 (ν1/2 226 Hz). At 238 K the
singlet narrows, shifts to δ -102.7 (ν1/2 112 Hz), and shows an
unresolved 1J(19F-117/119Sn) coupling of 668 Hz. The satellite-
to-signal-to-satellite integral ratio of 15.45:69.43:15.12 is close
to the calculated one of 17.16:65.68:17.16. This ratio as well
1
as the magnitude of the J(19F-117/119Sn) coupling confirms
the existence of a Sn-F-Sn bridge. (iii) The 119Sn NMR
spectrum of a solution of compound 9 in CDCl3 to which had
been added 1 molar equiv of potassium fluoride, KF, showed
two broad resonances at δ -105 (ν1/2 1550 Hz) and -153 (ν1/2
1230 Hz), which are low-frequency-shifted as compared to the
two singlets at δ -55 and -79 detected for compound 9. At
238 K decoalescence into two equally intense doublet resonances
at δ -99 [1J(119Sn-19F) 683 Hz] and -151 [1J(119Sn-19F) 692
Hz] was observed.
The ESI-MS also supports the identity of complex 9 · KF in
solution. In the positive mode there are mass clusters centered
atm/z1067,959,and791thatareassignedto{Ph2ISnCH2SnIPhCH2-
[19]-crown-6 · K}+, {Ph2ISnCH2SnPhCH2-[19]-crown-6 · KF}+,
and {Ph2SnCH2SnPhCH2-[19]-crown-6 · F}+, respectively.
(34) Dakternieks, D.; Jurkschat, K.; Zhu, H.; Tiekink, E. R. T.
Organometallics 1995, 14, 2512.
(35) Beckmann, J.; Horn, D.; Jurkschat, K.; Rosche, F.; Schu¨rmann,
M.; Zachwieja, U.; Dakternieks, D.; Duthie, A.; Lim, A. E. K. Eur. J. Inorg.
Chem. 2003, 164.
(36) Zuzuki, M.; Son, I. H.; Noyori, R.; Masuda, H. Organometallics
1990, 9, 3043.
(37) Wells, A. F. Structural Inorganic Chemistry, 4th ed.; Oxford
University Press: Oxford, 1975.
(38) Redman, J. E.; Beer, P. D.; Dent, S. W.; Drew, M. G. B. Chem.
Commun. 1998, 231.

5584 Organometallics, Vol. 27, No. 21, 2008
Tagne Kuate et al.
Analyzing the duplicate reflections showed no indication for any
decay. The structure was solved by direct methods with
SHELXS9740 and successive difference Fourier syntheses. Refine-
ment applied full-matrix least-squares methods with SHELXL97.41
The H atoms were placed in geometrically calculated positions
using a riding model with isotropic temperature factors constrained
at 1.2 for nonmethyl and at 1.5 for methyl groups times Ueq of the
carrier C atom.
Disordered crown ether rings were found in 2 with occupancies
of 0.5 (O(6), O(6′), C(33), C(33′)), in 3 with occupancies of 0.5
(O(4), O(4′)), and in 8 with occupancies of 0.4 (O(5), O(6), (C(32),
(C(33)) and 0.6 (O(5′), O(6′), (C(32′), (C(33′)).
Atomic scattering factors for neutral atoms and real and
imaginary dispersion terms were taken from International Tables
for X-ray Crystallography.42 The figures were created by SHELX-
TL.43 Crystallographic data are given in Table 5, selected bond
distances and angles for 1-4 in Tables 1 and 2, and those for 8,
9 · H2O, and 9 · KF in Tables 3 and 4.
Conclusions
The combination of the potassium cation-specific crown ether
[19]-crown-6 with mono- and ditin moieties, respectively,
provided novel host molecules that are capable of complexing
potassium thiocyanate, KSCN, and potassium fluoride, KF, in
ditopic fashion. The fact that in contrast to {Ph2FSnCH2-[16]-
crown-5}, which was shown to be unable to complex sodium
fluoride, the corresponding triorganotin fluoride {Ph2FSnCH2-
[19]-crown-6} complexes potassium fluoride, KF, is traced to
the lower lattice energy of the latter. With a variety of robust
organotin-substituted crown ethers now at hand, future work
will be devoted to explore the ability of these host molecules
to selectively transport salts through organic membranes.
Experimental Section
General Methods. Solvents were dried and distilled from the
appropriate desiccants prior to use. All manipulations were
performed under an inert atmosphere of nitrogen or argon. Literature
procedures were used to prepare 1,4,7,10,13,16-hexaoxacyclonona-
decane23 and triphenyltin hydride.39 The atom numbering of the
crown ether fragment is shown in Chart 3.
Synthesis of (1,4,7,10,13,16-Hexaoxacyclononadec-18-methyl)-
triphenylstannane (1). 18-Methylene-1,4,7,10,13,16-hexaoxacy-
clononadecane (5.12 g, 17.643 mmol) was mixed with triphenyltin
hydride, Ph3SnH (6.18 g, 17.643 mmol). After a small quantity of
AIBN (100 mg) had been added, the mixture was stirred at 60-80
°C for 15 h followed by cooling to room temperature. Addition of
CH2Cl2 (80 mL) followed by filtration through Celite and removal
of the solvent in vacuo afforded a viscous oil. Purification of the
oil by column chromatography with silica gel/CH2Cl2 and elution
with ethanol gave 8.06 g (71%) of 1 as a viscous oil, which
solidified after it had been kept a few days at room temperature,
mp 48 °C. Single crystals of 1 suitable for X-ray diffraction analysis
were obtained by slow evaporation of a solution of the compound
in CH2Cl2/n-hexane.
NMR Spectroscopy. NMR spectra were recorded on Bruker
DRX 500, DRX 400, and DPX 300, Varian Nova 600, and Varian
Mercury 200 spectrometers with broadband decoupling of 119Sn
at 111.92 MHz, 19F at 282.4 MHz, and 13C at 100.61 MHz.
Chemical shifts δ are given in ppm and referenced to tetrameth-
ylstannane (119Sn), CFCl3 (19F), and tetramethylsilane (1H, 13C).
Solid state 119Sn NMR spectra were recorded on a Bruker
AVANCE III 400 spectrometer equipped with a double-bearing
CP/MAS probe at room temperature. CP/MAS (cross-polarization/
magic angle spinning) experiments were used with a repetition delay
of 10s, and the contact time was set at 2 ms. Two spinning rates
(4000-7000 Hz) were used to identify the isotropic chemical sfift.
The number of scans varied between 500 and 1000. The 119Sn
chemical shifts were calibrated using tetracyclohexyltin (δ )
-97.35).
Complexation Studies. The samples for NMR analyses were
prepared by dissolving ca. 50 mg of the triorganotin halide and the
corresponding amounts of the potassium salt in deuterated solvents.
The potassium salts used for the complexation studies were dried
in vacuo (10-6 mbar) at 100 °C for one day and stored under
nitrogen.
Electrospray Mass Spectra. Spectra were recorded on a
Thermoquest-Finnigan instrument using CH3CN as the mobile
phase. The samples were introduced as solution in CH3CN via a
syringe pump operating at 0.5 µL/min. The capillary voltage was
4.5 kV, while the cone skimmer voltage varied between 50 and
250 kV. Identification of the expected 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.
3
1H NMR (CDCl3, 400.13 MHz) δ: 1.45 (d, J(1H-1H) ) 7.3
2
2
Hz, J(1H-117Sn) ) 51.5 Hz, J(1H-119Sn) ) 65.7 Hz, 2H, Sn-
CH2), 2.38 (m, 1H, CH), 3.28-3.71 (complex pattern, 24H, CH2-
O-CH2), 7.31-7.53 (15H, Ph). 13C{1H} NMR (CDCl3, 100.63
MHz) δ: 11.4 (1J(13C-117Sn) ) 398 Hz, J(13C-119Sn) ) 417
1
Hz, C20), 37.3 (2J(13C-117/119Sn) ) 20 Hz, C18), 70.2, 70.6, 70.7,
70.8, (C2-C15), 74.5 (3J(13C-117/119Sn) ) 48 Hz, C17/C19), 128.2
(3J(13C-117/119Sn) ) 49 Hz, Cm), 128.4 (4J(13C-117/119Sn) ) 12
Hz, Cp), 136.9 (2J(13C-117/119Sn)
) 36 Hz, Co), 140.2
(1J(13C-117Sn) ) 474 Hz, 1J(13C-119Sn) ) 496 Hz), Ci).
119Sn{1H} NMR (CDCl3, 111.93 MHz) δ: -106. Anal. Calcd for
C32H42O6Sn (641.39): C 59.9; H 6.6. Found: C 59.8; H 6.8.
Synthesis of Bromo(1,4,7,10,13,16-hexaoxacyclononadec-18-me-
thyl)diphenylstannane (2). To a cooled solution (-55 °C) of 1 (1.05
g, 1.637 mmol) in dichloromethane (30 mL) was added dropwise
a solution of bromine (0.26 g, 1.637 mmol) in dichloromethane
(15 mL). After the addition had been completed, the mixture was
stirred and warmed to room temperature overnight. From the clear
solution obtained, the solvent and the bromobezene formed were
removed in vacuo (10-3 mm Hg) to afford a light yellow solid,
which was recrystallized from ethanol to give 0.71 g (68%) of 2
as colorless crystals, mp 85 °C.
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 3 (2, 9 · H2O, 9 · KF), 4 (3), and 5 (1, 4, 8) sets at different
κ-angles with 513 (1), 263 (2), 454 (3), 421 (4), 512 (8), 272
(9 · H2O), and 249 (9 · KF) frames via ω-rotation (∆/ω ) 1°) at
two times 15 s (3, 9 · H2O), 40 s (1), 50 s (2), 70 s (4), 80 s (8),
and 150 s (9 · KF) per frame. The crystal-to-detector distance was
3.4 cm (1, 2, 4, 8, 9 · H2O, 9 · KF) and 4.4 cm (3). Crystal decay
was monitored by repeating the initial frames at the end of data
collection. The data were not corrected for absorption effects.
3
1H NMR (CDCl3, 400.13 MHz) δ: 1.69 (d, J(1H-1H) ) 8.04
2
2
Hz, J(1H-117Sn) ) 68.5 Hz, J(1H-119Sn) ) 83.6 Hz, 2H, Sn-
CH2), 2.56 (m, 1H, CH), 3.32-3.75 (complex pattern, 24H, CH2-
O-CH2), 7.34-7.77 (10H, Ph). 13C{1H} NMR (CDCl3, 100.63
MHz) δ: 18.9 (1J(13C-117Sn) ) 503 Hz, J(13C-119Sn) ) 527
1
Hz, C20), 37.4 (2J(13C-117/119Sn) ) 23 Hz, C18), 70.3, 70.5, 70.6,
70.8, 70.9 (C2-C15), 74.4 (3J(13C-117/119Sn ) 66 Hz, C17/C19),
(40) Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467.
(41) Sheldrick, G. M. SHELXL97; University of Go¨ttingen, 1997.
(42) International Tables for Crystallography; Kluwer Academic Pub-
lishers: Dordrecht, 1992; Vol. C.
(43) Sheldrick, G. M. SHELXTL, Release 5.1 Software Reference
Manual; Bruker AXS, Inc.: Madison, WI, 1997.
(39) Kuivila, H. G.; Beumel, O. F. J. Am. Chem. Soc. 1961, 83, 1246.

Organotin Compounds Ph2XSnCH2-[19]-crown-6
Organometallics, Vol. 27, No. 21, 2008 5585
Table 5. Crystallographic Data and Structure Refinements for Compounds 1-4, 8, 9 · H2O, and 9 · KF
1
2
3
4
8
9 · H2O
9 · KF
formula
fw
cryst syst
cryst size, mm
C
32H42O6Sn
C
26H37BrO6Sn
C
26H37IO6Sn
C
26H37ClO6Sn
C
39H49IO6Sn2
C
33H44I2O6Sn2 · H2O
C
33H44FI2KO6Sn2
641.35
triclinic
644.16
monoclinic
691.15
monoclinic
599.70
monoclinic
978.06
triclinic
1045.88
monoclinic
1085.96
monoclinic
0.10 × 0.10 ×
0.06
0.12 × 0.10 × 0.18 × 0.16 × 0.22 × 0.22 × 0.10 × 0.10 × 0.16 × 0.14 × 0.24 × 0.22 ×
0.10
0.16
P21/c
0.20
0.08
0.14
0.20
j
j
space group
a, Å
b, Å
P1
P21/c
P21/c
P1
P21/n
P21/c
13.7101(5)
14.2590(7)
15.8087(7)
80.987(18)
86.130(2)
87.754(2)
3044.1(2)
4
9.8780(5)
22.5904(14)
13.0178(5)
90
108.916(3)
90
2748.0(2)
4
1.557
10.0164(2)
22.4277(6)
13.1163(3)
90
109.6686(10)
90
2774.59(11)
4
1.655
9.8090(5)
22.6677(18)
12.9588(9)
90
108.653(4)
90
2730.0(3)
4
1.459
11.0743(6)
13.8150(10)
14.8912(14)
63.678(4)
87.735(6)
72.193(4)
1931.8(3)
2
12.3109(8)
23.0720(14)
13.6159(5)
90
103.304(3)
90
3763.6(4)
4
1.846
12.4106(15)
19.896(2)
15.6208(11)
90
94.869(7)
90
3843.2(7)
4
1.877
c, Å
R, deg
ꢀ, deg
γ, deg
V, Å3
Z
F
calcd, Mg/m3
1.399
0.880
1328
1.681
2.135
968
µ, mm-1
2.420
1304
2.070
1376
1.070
1232
3.009
2024
3.058
2096
F(000)
θ range, deg
2.93 to 25.35
3.26 to 27.45
3.19 to 27.51
2.91 to 27.47
2.95 to 27.45
3.06 to 25.35
2.62 to 25.34
-14 e h e 14
-23 e k e 23
-18 e l e 18
28 344
99.8
7010/0.054
2763
index ranges
-16 e h e 16 -12 e h e 12 -12 e h e 12 -12 e h e 12 -14 e h e 14 -14 e h e 14
-17 e k e 17 -29 e k e 29 -29 e k e 29 -29 e k e 29 -16 e k e 17 -27 e k e 24
-18 e l e 18
44 260
99.8
-16 e l e 15
22 494
99.3
6239/0.034
3669
-17 e l e 16
28 956
99.8
6345/0.031
4585
-16 e l e 15
36 315
99.8
6242/0.039
2831
-19 e l e 19
31 302
99.4
8794/0.036
4695
-16 e l e 16
28 815
99.8
6881/0.04
3329
no. of reflns collcd
completeness to θmax
no. of indep reflns/Rint
no. of reflns obsd with
I > 2σ(I)
11 135/0.022
8387
no. of refined params
703
325
0.862
0.0307
0.0614
0.001
316
1.091
0.0340
0.0872
0.001
302
0.801
0.0385
0.0886
0.001
469
0.739
0.0281
0.0469
0.001
397
0.657
0.0291
0.0468
0.000
406
0.517
0.0285
0.0509
0.000
GooF (F2)
0.936
0.0252
0.0539
0.001
R1(F) (I > 2σ(I))
wR2(F2) (all data)
(∆/σ)max
largest diff peak/hole, e/Å3 0.646/-0.542
1.027/-0.676
1.534/-0.907
1.163 /-0.806
0.660/-0.881
0.641/-1.012
0.861 /-0.617
128.6 (3J(13C-117/119Sn) ) 63 Hz, Cm), 129.4 (4J(13C-117/119Sn)
) 14 Hz, Cp), 135.8 (2J(13C-117/119Sn) ) 48 Hz, Co), 140.6
(1J(13C-117Sn) ) 617 Hz, 1J(13C-119Sn) ) 645 Hz), Ci).
119Sn{1H} NMR (CDCl3, 111.93 MHz) δ: -93. Anal. Calcd for
C26H37BrO6Sn (644.18): C 48.5; H 5.8. Found: C 48.5; H 5.5.
Synthesis of Iodo(1,4,7,10,13,16-hexaoxacyclononadec-18-me-
thyl)diphenylstannane (3). Over a period of 3 h, iodine (2.39 g,
9.355 mmol) was added in small portions at 0 °C to a stirred
solution of 1 (6.0 g, 9.355 mmol) in CH2Cl2 (100 mL). Stirring
was continued, and the reaction mixture was warmed to room
temperature overnight. Dichloromethane and iodobenzene were
removed in vacuo (10-3 mm Hg) to give a yellow solid. The latter
was recrystallized from ethanol at -5 °C to afford 5.26 g (81%)
of pure 3, mp 100 °C. Single crystals of 3 suitable for X-ray
diffraction analysis were obtained by slow evaporation of a solution
of the compound in ethanol.
for X-ray diffraction analysis were obtained by slow evaporation
of a solution of the compound in CH2Cl2/n-hexane.
3
1H NMR (CDCl3, 400.13 MHz) δ: 1.60 (d, J(1H-1H) ) 8.0
2
2
Hz, J(1H-117Sn) ) 70.5 Hz, J(1H-119Sn) ) 85.6 Hz, 2H, Sn-
CH2), 2.56 (m, 1H, CH), 3.34-3.75 (complex pattern, 24H, CH2-
O-CH2), 7.35-7.78 (10H, Ph). 13C{1H} NMR (CDCl3, 100.63
MHz) δ: 17.6 (1J(13C-117Sn) ) 515 Hz, J(13C-119Sn) ) 543
1
Hz, C20), 37.2 (2J(13C-117/119Sn) ) 23 Hz, C18), 70.3, 70.5, 70.6,
70.7, 70.8 (C2-C15), 74.4 (3J(13C-117/119Sn) ) 67 Hz, C17/C19),
128.6 (3J(13C-117/119Sn) ) 65 Hz, Cm), 129.4 (4J(13C-117/119Sn)
) 14 Hz, Cp), 135.8 (2J(13C-117/119Sn) ) 47 Hz, Co), 140.8
(1J(13C-117Sn) ) 634 Hz, 1J(13C-119Sn) ) 663 Hz), Ci).
119Sn{1H} NMR (CDCl3, 111.93 MHz) δ: -83. Anal. Calcd for
C26H37ClO6Sn (596.73): C 52.0; H 6.2. Found: C 51.5; H 6.2.
Synthesis of Fluoro(1,4,7,10,13,16-hexaoxacyclononadec-18-me-
thyl)diphenylstannane (5). A solution of 3 (2.0 g, 2.894 mmol) in
CH2Cl2 (20 mL) was mixed with a solution of NaF (1.22 g, 28.940
mmol) in water (30 mL). The biphasic mixture was stirred at room
temperature for 3 days. The organic phase was then separated and
dried over MgSO4. Removing the solvent in vacuo afford 1.02 g
(60%) of 5 as a colorless oil, which solidified after it had been
kept at room temperature for some days, mp 77 °C.
1H NMR (CDCl3, 400.13 MHz) δ: 1.46 (d, 3J(1H-1H) ) 9 Hz,
2J(1H-117Sn) ) 72.0 Hz, 2J(1H-119Sn) ) 87.0 Hz, 2H, Sn-CH2),
2.55 (m, 1H, CH), 3.42-3.77 (complex pattern, 24H, CH2-O-CH2),
7.38-7.78 (10H, Ph). 13C{1H} NMR (CDCl3, 100.63 MHz) δ: 13.9
(1J(13C-117/119Sn) ) 553 Hz, C20), 36.8 (2J(13C-117/119Sn) )
21 Hz, C18), 70.3, 70.4, 70.6, 70.7, 70.8 (C2-C15), 74.4
(3J(13C-117/119Sn) ) 65 Hz, C17/C19), 128.5 (3J(13C-117/119Sn)
) 63 Hz, Cm), 129.5 (4J(13C-117/119Sn) ) 14 Hz, Cp), 135.8
(2J(13C-117/119Sn) ) 47 Hz, Co), 140.6 (1J(13C-117Sn) ) 683 Hz,
1J(13C-119Sn) ) 713 Hz, Ci). 19F{1H} NMR (CDCl3, 282.4 MHz,
293 K) δ: -188.0 (1J(19F-117Sn) ) 2105 Hz,1J(19F-119Sn) )
2203 Hz). 119Sn{1H} NMR (CDCl3, 111.93 MHz) δ: -104 (d,
1J(119Sn-19F) ) 2200 Hz). Anal. Calcd for C26H37 FO6Sn (583.28):
C 53.8; H 6.4. Found: C 52.4; H.6.7.
3
1H NMR (CDCl3, 400.13 MHz) δ: 1.80 (d, J(1H-1H) ) 7.8
2
2
Hz, J(1H-117Sn) ) 65.0 Hz, J(1H-119Sn) ) 80.6 Hz, 2H, Sn-
CH2), 2.56 (m, 1H, CH), 3.31-3.76 (complex pattern, 24H, CH2-
O-CH2), 7.33-7.77 (10H, Ph). 13C{1H} NMR (CDCl3, 100.63
MHz) δ: 20.7 (1J(13C-117Sn) ) 481 Hz, J(13C-119Sn) ) 504
1
Hz, C20), 38.0 (2J(13C-117/119Sn) ) 25 Hz, C18), 70.3, 70.5, 70.6,
70.8, 70.9 ((C2-C15), 74.3 (3J(13C-117/119Sn) ) 65 Hz, C17/C19),
128.5 (3J(13C-117/119Sn) ) 63 Hz, Cm), 129.3 (4J(13C-117/119Sn)
) 14 Hz, Cp), 135.9 (2J(13C-117/119Sn) ) 47 Hz, Co), 140.1
(1J(13C-117Sn) ) 592 Hz, 1J(13C-119Sn) ) 620 Hz), Ci).
119Sn{1H} NMR (CDCl3, 111.93 MHz) δ: -126. 119Sn MAS NMR
(149.20 MHz) δ: -128. Anal. Calcd for C26H37IO6Sn (691.18): C
45.2; H 5.4. Found: C 45.2; H 5.4.
Synthesis of Chloro(1,4,7,10,13,16-hexaoxacyclononadec-18-me-
thyl)diphenylstannane (4). To a solution of 3 (0.50 g, 0.723 mmol)
in CH3CN (20 mL) was added excess silver chloride, AgCl (0.46
g, 3.210 mmol). The resulting mixture was stirred at room
temperature and in the dark for 14 days. After the AgI formed
and the nonreacted AgCl had been removed by filtration the
solvent was evaporated under vacuum. The slightly yellow oil
thus obtained was dissolved in ethanol and cooled at -5 °C to
give 0.38 g (88%) of pure 4, mp 65 °C. Crystals of 4 suitable

5586 Organometallics, Vol. 27, No. 21, 2008
Tagne Kuate et al.
Synthesis of Thiocyanato(1,4,7,10,13,16-hexaoxacyclononadec-
18-methyl)diphenylstannane (6). To a solution of 3(1.02 g, 1.476
mmol) in CH3CN (50 mL) was added excess AgSCN (0.73 g, 4.427
mmol). The reaction mixture was stirred at room temperature and
in the dark for 10 days, followed by filtration of the AgI formed
and the nonreacted AgSCN. Removing the solvent in vacuo gave
0.55 g (60%) of 6 as slightly yellow oil.
1J(13C-119Sn) ) 294 Hz, Sn-CH2-Sn), 20.6 (1J(13C-117Sn) ) 471
Hz, 1J(13C-119Sn) ) 494 Hz, SnCH2), 38.1 (2J(13C-117/119Sn) )
20 Hz, C18), 70.0, 70.7, 70.9, 71.0, 71.2, 71.3, 71.4 (C2-C15),
74.5/74.8 (C17/C19), 128.8 (3J(13C-117/119Sn) ) 60 Hz, SnIPh,
Cm), 128.9 (3J(13C-117/119Sn) ) 52 Hz, SnPh3, Cm), 129.4
(4J(13C-117/119Sn) ) 12 Hz, SnPh3, Cp), 129.6 (4J(13C-117/119Sn)
) 12 Hz, SnIPh2, Cp), 135.4 (2J(13C-117/119Sn) ) 48 Hz, SnIPh,
Co), 137.7 (2J(13C- 117/119Sn) ) 39 Hz, SnPh3, Co), 139.7
3
1H NMR (CDCl3, 400.13 MHz) δ: 1.59 (d, J(1H-1H) ) 4.0
(3J(13C-117/119Sn)
) ) 497 Hz,
14 Hz, 1J(13C-117Sn)
2
2
Hz, J(1H-117Sn) ) 68.0 Hz, J(1H-119Sn) ) 84.0 Hz, 2H, Sn-
CH2), 2.57 (m, 1H, CH), 3.44-3.76 (complex pattern, 24H, CH2-
O-CH2), 7.43-7.76 (10H, Ph). 13C{1H} NMR (CDCl3, 100.63
MHz) δ: 15.4 (C20), 37.4 (C18), 70.8, 70.9, 71.0, 71.2 (C2-C15),
75.1 (C17/C19), 128.3 (3J(13C-117/119Sn) ) 65 Hz, Cm), 130.3
(Cp), 136.3 (2J(13C-117/119Sn) ) 45 Hz, Co), 139.1 (Ci). 119Sn{1H}
NMR (CDCl3, 111.93 MHz) δ: -154 (t, 1J(119Sn-14N) ) 256 Hz).
Anal. Calcd for C27H37 NO6SSn (596.73): C 52.1; H 6.0; N 2.3.
Found: C 51.4; H 5.7; N 2.6.
1J(13C-119Sn) ) 521 Hz, SnPh3, Ci), 143.4 (3J(13C-117/119Sn) )
22 Hz, 1J(13C-117Sn) ) 547 Hz, 1J(13C-119Sn) ) 572 Hz, SnIPh2,
Ci). 119Sn{1H} NMR (CDCl3, 111.92 MHz) δ: -62 (2J (119Sn-117/
119Sn) ) 293/310 Hz, SnPh3), -85 (2J(119Sn-117/119Sn) ) 294/
312 Hz, SnIPh). Anal. Calcd (%) for C39H49IO6Sn2 (977.98): C
47.9, H 5.0. Found: C 48.1, H 4.9.
Synthesis of the Aqua Complex of 18-({Iodophenyl[(iododi-
phenylphenylstannyl)methyl]stannyl}methyl)-1,4,7,10,13,16-hexaox-
anonadecane (9 · H2O). Iodine (0.55 g, 2.154 mmol) was added
in small portions and under ice cooling to a stirred solution of
7 (1.0 g, 1.077 mmol) in CH2Cl2 (50 mL). The reaction mixture
was stirred while warming at room temperature overnight. The
solvent and the iodobenzene were removed in vacuo (10-3 mm
Hg) to afford a yellow oil. The oil was dissolved in ether (10
mL), and the solution was cooled at -20 °C for several days to
give 0.7 g (63%) of 9 as a yellow solid. Single crystals of 9 · H2O
(mp 68-70 °C) suitable for X-ray diffraction analysis were
obtained by slow evaporation of an ethanol solution of 9 at room
temperature.
Synthesis of 18-({Diphenyl[(triphenylstannyl)methyl]stannyl}me-
thyl)-1,4,7,10,13,16-hexaoxanonadecane (7). A solution of (bro-
momagnesiummethyl)triphenylstannane, prepared from (bro-
momethyl)triphenylstannane (2.27 g, 5.113 mmol) and magnesium
(0.13 g, 5.349 mmol) in THF (60 mL), wad added dropwise to
a stirred solution of iodo({1,4,7,10,13,16-hexaoxanonadec-18-
yl}methyl)diphenylstannane (3.0 g, 4.340 mmol) in THF (50
mL) for a period of 2 h. After the addition had been completed,
the reaction mixture was heated at reflux overnight and then
cooled to room temperature. Cold water (60 mL) was added,
and the mixture was extracted three times with 50 mL of ether.
The combined organic phases were dried with MgSO4 and the
solvents evaporated in vacuo to give the crude product. It was
purified by column chromatography (Al2O3, CH2Cl2, ethyl
acetate) to yield 1.11 g (27.5%) of 7 as a colorless oil.
1H NMR (CDCl3, 400.13 MHz) δ: 1.12/1.49 (ABX-type
resonance, 2J(1H-1H) ) 11.5 Hz, 3J(1H-1H) ) 7.1 Hz, 2H,
Sn-CH2), 1.73/1.93 (AB-type resonance, 2J(1H-1H) ) 11.3 Hz,
2J(1H-117Sn) ) 56.7 Hz, 2J(1H-119Sn) ) 78.0 Hz, 2H, Sn-
CH2-Sn), 2.24 (1H, CH), 3.21-3.64 (complex pattern, 24H, CH2-
O-CH2), 7.29-7.81 (15H, Ph). 13C NMR (CDCl3, 100.63 MHz)
δ: 4.0 (1J(13C-117Sn) ) 288/301 Hz, 1J(13C-119Sn) ) 324/
1H NMR (CDCl3, 400.13 MHz) δ: 0.81 (s, 2J(1H-117/119Sn) )
61.7 Hz, 2H, Sn-CH2-Sn), 1.01 (d, 3J(1H-117/119Sn) ) 7.5 Hz,
2
2J(1H-117Sn) ) 48 Hz, J(1H-119Sn) ) 64.0 Hz, 2H, Sn-CH2),
339 Hz, Sn-CH2-Sn), 20.9 (1J(13C-117Sn)
) 483 Hz,
2.13 (m, 1H, CH), 3.21-3.68 (complex pattern, 24H, CH2-O-CH2),
7.22-7.47 (25H, Ph). 13C NMR (CDCl3, 100.63 MHz) δ: -15.2
(1J(13C-117Sn) ) 262/273 Hz, 1J(13C-119Sn) ) 287/300 Hz, Sn-
1J(13C-119Sn) ) 505 Hz, SnCH2), 38.2 (2J(13C-117/119Sn) )
25 Hz, C18), 70.8, 71.0, 71.2, 71.3 (C2-C15), 74.5 (C17/C19),
129.0 (3J(13C-117/119Sn) ) 62 Hz, SnIPh, Cm), 129.2 (3J(13C-117/
119Sn) ) 63 Hz, SnIPh2, Cm), 129.8 (4J(13C-117/119Sn) ) 13
Hz, SnIPh, Cp), 130.4 (4J(13C-117/119Sn) ) 14 Hz, SnIPh2, Cp),
135.5 (2J(13C-117/119Sn) ) 48 Hz, SnIPh, Co), 137.0 (SnIPh2,
Co), 138.4 (SnIPh, Ci), 142.1 (3J(13C-117/119Sn) ) 28 Hz, SnIPh,
Ci). 119Sn{1H} NMR (CDCl3, 111.92 MHz) δ: -55 (2J (119Sn-117/
119Sn) ) 256 Hz, SnIPh2), -79 (2J(119Sn-117/119Sn) ) 261 Hz,
SnIPh). 119Sn MAS NMR (149.20 MHz) δ: -67, -171. Anal.
Calcd (%) for C33H44I2O6Sn2 · H2O (1045.94): C 37.9, H 4.4.
Found: C 37.8, H 4.3.
1
CH2-Sn), 12.5 (1J(13C-117Sn) ) 388 Hz, J(13C-119Sn) ) 406
Hz, SnCH2), 37.6 (2J(13C-117/119Sn) ) 19 Hz, C18), 70.8, 71.1,
71.2, 71.3 (C2-C15), 75.1 (C17/C19), 74.6 (3J(13C- 117/119Sn)
) 50 Hz, C17/C19), 128.5 (3J(13C-117/119Sn) ) 48 Hz, SnPh2,
Cm), 128.7 (SnPh2, Cp), 128.8 (3J(13C-117/119Sn) ) 48.3 Hz, SnPh3,
Cm), 129.1 (4J(13C-117/119Sn) ) 11 Hz, SnPh3, Cp), 136.9
(2J(13C-117/119Sn) ) 37 Hz, SnPh2, Co), 137.3 (2J(13C-117/119Sn)
) 38 Hz, SnPh3, Co), 140.2 (3J(13C-117/119Sn) ) 9 Hz,
1
1J(13C-117Sn) ) 483 Hz, J(13C-119Sn) ) 505 Hz, SnPh3, Ci),
142.2 (3J(13C-117/119Sn) ) 12 Hz, 1J(13C-117Sn) ) 457 Hz,
1J(13C-119Sn) ) 479 Hz, SnPh2, Ci). 119Sn{1H} NMR (CDCl3,
111.92 MHz) δ: -55 (2J(119Sn-117/119Sn) ) 231 Hz, SnPh2), -76
(2J(119Sn-117/119Sn) ) 227 Hz, SnPh3). Anal. Calcd (%) for
C45H54O6Sn2 (928.34): C 58.2, H 5.9. Found: C 58.2, H 6.0.
Synthesis of 5 · KF. Potassium fluoride (7.6 mg, 0.130 mmol)
was added to a solution of 5 (75.86 mg, 0.130 mmol) in CH2Cl2
(7 mL), and the mixture was stirred at room temperature for 2
days. The reaction mixture was filtered, and the filtrate was dried
over molecular sieves. n-Hexane (5 mL) was added, and slow
evaporation of the solvent gave 42.5 mg (51%) of 5 · KF as a
colorless crystalline solid, mp 230 °C. 1H NMR (CDCl3, 400.13
MHz, 293 K) δ: 1.26 (d, 3J(1H-1H) ) 8.0 Hz, 2J(1H-117/119Sn)
) 82.8 Hz, 2H, Sn-CH2), 2.55 (m, 1H, CH), 3.36-3.64 (complex
pattern, 24H, CH2-O-CH2), 7.28-8.16 (10H, Ph). 13C{1H} NMR
(CDCl3,100.63 MHz, 293 K) δ: 19.4 (C20), 36.0 (C18), 69.7,
69.8, 69.9, 70.2 (C2-C15), 76.4 (C17/C19), 127.6 (3J(13C-117/
119Sn) ) 67 Hz, Cm), 128.1 (Cp), 136.6 (2J(13C-117/119Sn) )
49 Hz, Co), 145.9 (broad, Ci). 19F{1H} NMR (CDCl3, 282.4
MHz, 293 K) δ: -157.7 (1J(19F-117Sn) )1838 Hz,
1J(19F-119Sn) ) 1912 Hz). 119Sn{1H} NMR (CDCl3, 111.92
MHz, 293 K) δ: - 277 (t, 1J(119Sn-19F) ) 1919 Hz). Anal.
Calcd (%) for C26H37F2KO6Sn (641.38): C 48.7, H 5.8. Found:
C 48.3, H 6.2.
Synthesis of 18-({Iodophenyl[(triphenylphenylstannyl)methyl]-
stannyl}methyl)-1,4,7,10,13,16-hexaoxanonadecane (8). Iodine (107.1
mg, 0.422 mmol) was added in small portions and under ice
cooling to a stirred solution of 7 (392.0 mg, 0.422 mmol) in
CH2Cl2 (20 mL). Stirring was continued while warming to room
temperature overnight. The solvent and the iodobenzene were
removed in vacuo (10-3 mmHg) to afford a slightly yellow oil.
The oil was dissolved in ethanol (8 mL), and the solution was
cooled at -15 °C for some days to give 260.0 mg (60.2%) of 8
as a colorless crystalline solid, mp 88-90 °C.
1H NMR (CDCl3, 400.13 MHz) δ: 0.91 (dd, 2J(1H-1H) ) 13.1
3
Hz, J(1H-1H) ) 6.5 Hz, 1H, Sn-CHH′), 1.25-1.46 (m, 3H, Sn-
CHH′-Sn and Sn-CH2-Sn), 2.10 (m, 1H, CH), 3.14-3.76 (complex
pattern, 24H, CH2--O-CH2), 7.34-7.76 (20H, Ph). 13C NMR
(CDCl3, 100.63 MHz) δ: -5.7 (1J(13C-117Sn) ) 282 Hz,

Organotin Compounds Ph2XSnCH2-[19]-crown-6
Organometallics, Vol. 27, No. 21, 2008 5587
Synthesis of 6 · KSCN. A solution of potassium thiocyanate
(175.0 mg, 1.801 mmol) in water (6 mL) was mixed with a
solution of 4 (83.3 mg, 0.139 mmol) in CH2Cl2 (6 mL). The
biphasic mixture was stirred at room temperature for 2 days.
The organic phase was separated and dried over molecular sieves
for 24 h. After the molecular sieves had been filtered the solvent
was removed in vacuo to give 0.086 g (86%) of 6 · KSCN as a
colorless oil. 1H NMR (CDCl3, 400.13 MHz, 293 K) δ: 1.52
(broad, 2J(1H-117/119Sn) ) 75.0 Hz, 2H, Sn-CH2), 2.55 (m, 1H,
CH), 3.39-3.60 (m, 24H, CH2-O-CH2), 7.33-8.06 (m, 10H, Ph).
13C{1H} NMR (CDCl3, 100.63 MHz, 293 K) δ: 23.6 (C20), 38.0
(C18), 70.1, 70.2, 70.4, 70.8 (C2-C15), 78.6 (broad, C17/C19,),
128.6 (3J(13C-117/119Sn) ) 69 Hz, Cm), 129.2 (Cp), 136.9
(2J(13C-117/119Sn) ) 48 Hz, Co), 142.5 (Ci). 119Sn{1H} NMR
(CDCl3, 111.92 MHz, 293 K) δ: -246. Anal. Calcd for
C28H37N2KO6S2Sn (725.55): C 46.7; H 5.2; N 3.9. Found: C
47.0; H 5.5; N 3.4.
Complexation Studies. In Situ Reaction of 2 with 1 equiv
of KBr in CD3CN/D2O (4:1). KBr (9.3 mg, 0.078 mmol) was
added to a solution of 2 (50.0 mg, 0.078 mmol) in CD3CN/D2O
(4:1). 119Sn{1H} NMR (111.92 MHz, 293 K) δ: -105.
In Situ Reaction of 2 with 3 equiv of KBr in CD3CN/D2O
(7:1). KBr (18.6 mg, 0.156 mmol) was added to a solution of 2
(50 mg, 0.078 mmol) in CD3CN/D2O (7:1). 119Sn{1H} NMR
(111.92 MHz, 293 K) δ: -125.
In Situ Reaction of 3 with 1 equiv of KI in CD3CN/D2O
(4:1). KI (12.0 mg, 0.072 mmol) was added to a solution of 3 (50.0
mg, 0.072 mmol) in CD3CN/D2O (4:1). 119Sn{1H} NMR (111.92
MHz, 293 K) δ: -124.
In Situ Reaction of 4 with 1 equiv of KCl in CD3CN/D2O
(7:1). KCl (6.3 mg, 0.084 mmol) was added to a solution of 4 (50.0
mg, 0.084 mmol) in CD3CN/D2O (7:1). 119Sn{1H} NMR (111.92
MHz, 293 K) δ: -122.
In Situ Reaction of 4 with 2 equiv of KCl in CD3CN/D2O
(8:1). KCl (12.6 mg, 0.168 mmol) was added to a solution of 4
(50 mg, 0.084 mmol) in CD3CN/D2O (8:1). 119Sn{1H} NMR
(111.92 MHz, 293 K) δ: -130.
Synthesis of 9 · KF. Potassium fluoride (1.3 mg, 1.95 × 10-5
mol) was added to a methanol solution of 9 · H2O (20.0 mg, 1.95
× 10-5 mol) at room temperature, and the mixture was stirred
for 30 min. The solvent was allowed to completely evaporate at
ambient temperature to give a yellow solid residue. This residue
was dissolved in dichloromethane, and the solution was filtered.
Slow diffusion of the CH2Cl2 solution with ether gave 11 mg
(51.4%) of 9 · KF as a yellow crystalline solid, mp 185 °C. Anal.
Calcd (%) for C33H44FI2KO6Sn2 (1086.02): C 36.5, H 4.1. Found:
In Situ Reaction of 5 with 1 equiv of n-Bu4NF in CDCl3.
n-Bu4NF (32.4 mg, 0.103 mmol) was added to a solution of 5 (59.9
mg, 0.103 mmol) in CDCl3. 19F{1H} NMR (282.4 MHz, 293 K)
δ: -150.0 (1J(19F-117/119Sn) ) 1809.0 Hz), -187. 119Sn{1H}
NMR (111.92 MHz, 293 K) δ: -267.0 (t, 73%, 1J(117/119Sn-19F)
1
) 1860.0 Hz), -106 (d, 27%, J(117/119Sn-19F) ) 2084.0 Hz).
1
C 36.8, H 3.9. H NMR (CDCl3, 400.13 MHz, 293 K) δ: 1.05
Acknowledgment. A.C.T.K. is grateful to the Deutsche
Akademische Austauschdienst (DAAD) for a scholarship.
We thank Dr. Gerrit Bradtmo¨ller for recording selected NMR
spectra and Mrs. Sylvia Marzian from TU Dortmund for
recording the electrospray mass spectra.
(2J(1H-1H) ) 6.3 Hz, 2J(1H-117/119Sn) ) 68.5 Hz, 2H, Sn-
CH2), 1.41 (2J(1H-117/119Sn) ) 76.5 Hz, 2H, Sn-CH2-Sn), 2.24
(1H, CH), 3.29-3.49 (complex pattern, 24H, CH2-O-CH2),
7.24-7.97 (15H, Ph). 19F{1H} NMR (CDCl3, 282.4 MHz) 293
K: δ -105 (broad, ν1/2 ) 226 Hz), 238 K: δ -102.7
(1J(19F-117Sn) ) 668 Hz. 119Sn{1H} NMR (111.92 MHz) 293
K: δ -105 (broad, ν1/2 ) 1550 Hz), -153 (broad, ν1/2 ) 1230
Hz); 238 K: δ -99 (d, 1J(119Sn-19F) ) 683 Hz), -151(d,
1J(119Sn-19F) ) 692 Hz).
Supporting Information Available: This material is available
free of charge via the Internet at http://pubs.acs.org.
OM800450K