Intramolecularly coordinated bis(crown ether)-substituted organotin halides as ditopic salt receptors

Article abstract of DOI:10.1021/om400216z

The synthesis of the bis(crown ether)-substituted organostannanes X ₂Sn(CH₂-[16]-crown-5)₂ (3, X = I; 4, X = Br; 5, X = Cl; 6, X = F) and X₂Sn(CH₂-[13]-crown-4)₂ (10, X = I; 11, X = Br; 12, X = F) is reported. The compounds have been characterized by ¹H, ¹³C, ¹⁹F, and ¹¹⁹Sn NMR spectroscopy, elemental analyses, and electrospray ionization mass spectrometry (ESI-MS). Single-crystal X-ray diffraction analyses reveal a distorted-octahedral cis,cis,trans configuration of the tin atoms in compounds 4-6 and 10-12 as a result of intramolecular O→Sn coordination. The ability of the host molecules to form mono- and ditopic complexes with various halide salts in different solvents, including water, has been investigated by NMR spectroscopy and ESI-MS.

Full text of DOI:10.1021/om400216z

Article
pubs.acs.org/Organometallics
Intramolecularly Coordinated Bis(crown ether)-Substituted
Organotin Halides as Ditopic Salt Receptors
Verena Arens,† Christina Dietz,† Dieter Schollmeyer,‡ and Klaus Jurkschat*,†
†Lehrstuhl fur Anorganische Chemie II, Technische Universitat Dortmund, D-44221 Dortmund, Germany
̈
̈
‡Institut fur Organische Chemie, Johannes Gutenberg Universitat Mainz, Duesbergweg 10-14, D-55099 Mainz, Germany
̈
̈
S
* Supporting Information
ABSTRACT: The synthesis of the bis(crown ether)-sub-
stituted organostannanes X2Sn(CH2-[16]-crown-5)2 (3, X = I;
4, X = Br; 5, X = Cl; 6, X = F) and X2Sn(CH2-[13]-crown-4)2
(10, X = I; 11, X = Br; 12, X = F) is reported. The compounds
1
have been characterized by H, 13C, 19F, and 119Sn NMR
spectroscopy, elemental analyses, and electrospray ionization
mass spectrometry (ESI-MS). Single-crystal X-ray diffraction
analyses reveal a distorted-octahedral cis,cis,trans configuration
of the tin atoms in compounds 4−6 and 10−12 as a result of
intramolecular O→Sn coordination. The ability of the host molecules to form mono- and ditopic complexes with various halide
salts in different solvents, including water, has been investigated by NMR spectroscopy and ESI-MS.
binding site, were reported by our group in the last few
years.13−15,16a To the best of our knowledge, the only examples
containing two crown ether moieties attached to one tin atom
are diorganotin dicarboxylates of the type n-Bu2Sn(OCOR)2 (R
= benzo-18-crown-6, benzo-15-crown-5) (G in Chart 1), the
complexation properties of which toward salts were, however,
not investigated.16b In a continuation of our systematic studies
on organotin-substituted crown ethers we report here bis-
(crown ether)-substituted organotin halides of type H (Chart
1) and investigations of the complexation behavior of these
compounds toward different halide salts in different solvents.
INTRODUCTION
■
Ditopic receptors are molecules that complex the cation as well
as the anion of an ion pair. Such molecules have attracted
increasing interest in the last two decades, because it has been
noticed that the complexation of ions by host molecules
depends on the identity and the concentration of counterions:
that is to say, the interaction of host molecules with their guests
can be restricted by ion pair effects. Consequently, the use of
ion pair receptors should lead to higher affinities and improved
selectivity in comparison to that of monotopic receptors.
However, while the development of receptors for cations or
anions started in the late 1960s,1−4 the first artificial receptor
for ion pairs was reported in 1991.5 This is due to challenges in
synthesizing these host molecules and to the complexity of the
several component mixtures arising from their application as
ditopic receptors. However, in recent years the simultaneous
complexation of anions and cations by ditopic receptors has
become a well-established area in host−guest chemistry. This is
evidenced by numerous publications and reviews reporting
different strategies of ion pair recognition.6−10 However, there
are only a few examples of ditopic receptors containing Lewis-
acidic organoelement or organometallic centers, as most of the
published host molecules are merely organic compounds,
despite the fact that the first representative of this class of
compounds was the organoboron-substituted crown ether A
(Chart 1) Receptor A,5 the analogous organoaluminum
compound B,11 and the organotin-substituted crown ether
C12 are able to bind potassium fluoride (KF), lithium fluoride
(LiF), and sodium thiocyanate (NaSCN) as separate ions but
suffer from their instability under noninert conditions, limiting
their potential applications (Chart 1). More robust ditopic
receptors of types D−F (Chart 1), applying kinetically inert
Sn−C bonds to link the organotin moiety with the cation
RESULTS AND DISCUSSION
■
Synthetic Aspects and Molecular Structures in the
Solid State. The synthesis of compounds 1−6 is summarized
in Scheme 1. The reaction of iodido(1,4,7,10,13-pentaoxahex-
adec-15-ylmethyl)diphenylstannane14 with LiAlH4 provided the
mono(crown ether)-substituted triorganohydridostannane 1.
Hydrostannation at 70 °C of 15-methylene-1,4,7,10,13-
pentaoxacyclohexadecane with triorganohydridostannane 1
gave the bis(crown ether)-substituted tetraorganostannane 2.
The diorganotindihalide derivatives 3−5 were obtained by the
reaction of the tetraorganostannane 2 with 2 molar equiv of
iodine (I2), bromine (Br2), or iodine chloride (ICl),
respectively. The diorganodifluoridostannane 6 was obtained
in dichloromethane at room temperature by treatment of the
diorganodiiodidostannane 3 with 2 molar equiv of silver
fluoride (AgF). The preparation of compounds 8−12 is
analogous to that of compounds 1−4 and 6 (Scheme 1). The
reaction of the triorganobromidostannane 7, which had been
Received: March 14, 2013
Published: April 23, 2013
© 2013 American Chemical Society
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Chart 1
a
Scheme 1.
a
Conditions: (i) LiAlH4, Et2O, 0 °C; (ii) 15-methylene-1,4,7,10,13-pentaoxacyclohexadecane, aibn, 70 °C; (iii) for X = I, 2 I2, CH2Cl2, 0 °C, −2 PhI;
(iv) for X = Br, 2 Br2, CH2Cl2, −2PhBr; (v) 2 ICl, CH2Cl2, 0 °C, −2 PhI; (vi) 2 AgF, CH2Cl2/H2O, room temperature, −2 AgI.
prepared by the addition of 1 equiv of bromine at low
temperatures to (1,4,7,10-tetraoxacyclotridec-12-ylmethyl)-
triphenylstannane,16 with LiAlH4 afforded triorganohydridos-
tannane 8. Hydrostannation of 12-methylene-1,4,7,10-tetraox-
acyclotridecan with the triorganohydridostannane 8 gave the
tetraorganostannane 9. The diorganodiiodidostannane 10 and
the diorganodibromidostannane 11 were obtained by the
reaction of the tetraorganostannane 9 with 2 equiv of iodine
(I2) and bromine (Br2), respectively, while the diorganodi-
fluoridostannane 12 was produced by reacting the diorgano-
diiodido derivative 10 with 2 molar equiv of silver fluoride
(AgF).
While the tri- and tetraorganotin compounds 1, 2, 8, and 9
are viscous oils, the diorganodiiodidostannane 3 solidified after
standing for several weeks at room temperature. The
diorganotin dihalide derivatives 4−7 and 10−12 are colorless
to slightly yellow solids. The triorganohydridostannane 1 is well
soluble in benzene and chloroform. Compounds 2−7 and 10−
12 are readily soluble in dichloromethane, chloroform, toluene
and benzene, display moderate solubility in acetonitrile, hexane,
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Figure 1. Molecular structure of the diorganodibromidostannane 4 showing 30% probability displacement ellipsoids and crystallographic numbering
1
scheme. The hydrogen atoms are omitted for clarity. Symmetry operation for generation of symmetry-equivalent atoms: (A) −x, y, −z + /2.
and alcohols, and have sufficient solubility in water to record
1H NMR spectra.
Å (4) and 2.5598(14) Å (5) and are much shorter than the sum
of the van der Waals radii17 of tin (2.17 Å) and oxygen (1.50
Å). The distances are slightly longer than in the crown ether
substituted diorganotin dihalides X2PhSn-CH2-[16]-crown-5
(X = Cl, 2.522(1)/2.4793(9) Å; X = I, 2.482(2) Å)14 or the
intramolecularly coordinated diorganotin dihalide
(H3COOCC2H4)2SnBr2 (2.529(3)/2.533(3) Å).18 The Sn−X
bonds (4, X = Br, 2.5552(4) Å; 5, X = Cl, 2.4067(6) Å; 6, X =
F, 1.9610(13) Å) are longer than in the tetracoordinated
dicyclohexyltin dihalides (C6H11)2SnX2 (X = Br, 2.516(2)/
2.492(3) Å; X = Cl, 2.393(4)/2.400(5) Å)19a and diphenyltin
dibromide, Ph2SnBr2 (2.4710(3)/2.4947(9) Å)19b but shorter
than in the intermolecularly coordinated diorganotin dihalide
Me2SnX2·2(N-methylpyrrolidine) (X = Br, 2.6738(10)/
2.6761(12) Å; X = Cl, 2.4737(7)/2.4768(8) Å).20
As a representative of compounds 4−6 the molecular
structure of the diorganodibromidostannane 4 as determined
by single-crystal X-ray diffraction analysis is shown in Figure 1.
The compounds 5 and 6 are isostructural with compound 4,
and their structures are given in the Supporting Information
(Figures S1 and S2). Selected bond lengths and bond angles of
compounds 4−6 are summarized in Tables 1 and 2. One of the
Table 1. Selected Bond Lengths (Å) in Compounds 4−6
4 (X = Br)
5 (X = Cl)
6 (X = F)
Sn(1)−C(1)
Sn(1)−X(1)
Sn(1)−O(1)
2.136(2)
2.117(2)
2.102(2)
2.5552(4)
2.5752(19)
2.4067(6)
2.5598(14)
1.9610(13)
2.5672(16)
As result of the cis orientation of the oxygen and the halogen
atoms the crown ether moieties are on the same side of the
molecule, thus forming a butterfly-like structure. This arrange-
ment suggests that the two crown ether moieties should be able
to complex one larger cation, which prefers a higher
coordination number, instead of two sodium cations.
Table 2. Selected Bond Angles (deg) for Compounds 4−6
4 (X = Br)
5 (X = Cl)
6 (X = F)
C(1A)−Sn(1)−C(1)
C(1A)−Sn(1)−X(1A)
C(1)−Sn(1)−X(1A)
X(1A)−Sn(1)−X(1)
C(1)−Sn(1)−O(1A)
C(1A)−Sn(1)−O(1A)
X(1)−-Sn(1)−O(1)
X(1)−Sn(1)−O(1A)
O(1A)−Sn(1)−O(1)
141.74(16)
107.97(8)
98.26(8)
92.77(2)
82.90(9)
72.79(9)
84.33(5)
169.08(4)
100.39(9)
142.69(11)
107.41(6)
98.12(6)
92.99(3)
83.15(7)
72.97(7)
84.49(3)
169.41(3)
99.80(7)
144.53(12)
105.90(8)
98.41(7)
92.77(9)
84.31(8)
72.39(7)
85.72(6)
169.79(6)
97.52(7)
The molecular structure of diorganodibromidostannane 11 is
shown in Figure 2; those of the iodido- and fluorido-substituted
compounds 10 and 12 are given in the Supporting Information
(Figures S3 and S4). Selected bond lengths and bond angles of
compounds 10−12 are summarized in Tables 3 and 4. One
crown ether moiety, one halogen atom, and half of the tin atom
in compounds 10 and 11 are created by a C2 axis. The structure
of compound 10 is isostructural with that of 11, while that of
12 is very similar to that of 10 and 11 but lacks the C2
symmetry. In all three structures the tin atoms, being
surrounded by two halogen atoms, two crown ether oxygen
atoms, and two crown ether carbon atoms, feature a distorted-
octahedral cis,cis,trans environment. The distortion is man-
ifested by (i) the decrease of the C(1)−Sn(1)−C(1A)/C(101)
angles from 180° to 153.4(2)° (10), 155.6(1)° (11), and
145.70(12)° (12), (ii) the decrease of the O(1)−Sn(1)−
O(1A) angles from 90° to 88.59(11)° (10) and 87.59(9)° (11)
and the increase of the O(1)−Sn(1)−O(101) angle from 90°
to 115.14(7)° (12), and (iii) the decrease of the X(1)−Sn(1)−
O(1A)/O(101) angles from 180° to 173.41(6)° (10),
171.27(4)° (11), and 164.58(7)° (12).
crown ether moieties, one halogen atom, and half of the tin
atom are created by symmetry through a C2 axis. The tin atoms
in compounds 4−6 show distorted-octahedral cis,cis,trans
environments and are surrounded by two halogen atoms, two
crown ether oxygen atoms, and two crown ether carbon atoms.
The distortion is most perceivable by (i) the decrease of the
C(1)−Sn(1)−C(1A) angles from 180° to 141.74(16)° (4),
142.69(11)° (5), and 144.53(12)° (6), (ii) the increase of the
O(1)−Sn(1)−O(1A) angles from 90° to 100.39(9)° (4),
99.80(7)° (5), and 97.52(7)° (6), and (iii) the decrease of the
X(1)−Sn(1)−O(1A) angles from 180° to 169.08(4)° (4),
169.41(3)° (5), and 169.79(6)° (6). The intramolecular
Sn(1)−O(1) distances fall in the range between 2.5752(19)
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The crown ether moieties in these three compounds display
a parallel arrangement. The distance between the crown ether
rings is approximately that of the crown ether diameter (5−8
Å). Thus, a cavity is formed that holds potential for the
complexation of larger cations.
Structures in Solution. The 119Sn NMR spectra of the
1
triorganohydridostannanes 1 (δ −147, J(119Sn−1H) = 1903
1
Hz) and 8 (δ −147, J(119Sn−1H) = 1921 Hz) and of the
tetraorganostannanes 2 (δ −82) and 9 (δ −78) display single
resonances. Their chemical shifts are comparable to those of
1
triphenylhydridostannane (Ph3SnH; δ −148, J(119Sn−1H) =
1936 Hz),21 dineohexyldiphenylstannane (δ −64), and
dicyclohexyldiphenylstannane (δ −107),22 thus indicating
tetracoordinated tin atoms.
The 119Sn NMR spectra of the organotinhalide derivatives
3−7 and 10−12 display resonances at δ −221 (3), −137 (4),
−112 (5), −236 (6), −96 (7), −227 (10), −135 (11) and
−235 (12). These resonances are shifted to low frequency in
comparison to those of tetracoordinated diorganotin dihalides
(Me2SnI2, δ −159;23 t-Bu2SnBr2, δ 77;24 t-Bu2SnCl2, δ 5625),
indicating retention of the intramolecular O→Sn coordination
in solution. The 119Sn NMR signals of the difluorido-
substituted compounds 6 and 12 are triplets, indicating
kinetically inert Sn−F bonds on the 119Sn NMR time scale.
As the 119Sn NMR signals of the other diorganotindihalide
compounds 4, 5, 7, 10, and 11 are sharp, it is assumed that their
Sn−X bonds are also kinetically inert.
Figure 2. Molecular structure of diorganodibromidostannane 11
showing 30% probability displacement ellipsoids and crystallographic
numbering scheme. The hydrogen atoms and the disordered bromine
and tin atoms are omitted for clarity. Symmetry operation for
1
generation of symmetry-equivalent atoms: (A) −x + 1, y, −z + /2.
1
The H and 13C NMR spectra suggest hypercoordination of
Table 3. Selected Bond Lengths (Å) in Compounds 10−12
the tin atoms as well. As a representative, the spectra of the
1
10 (X = I)
11 (X = Br)
12 (X = F)
diorganotin difluoride 6 are discussed here. In the H NMR
Sn(1)−C(1)
Sn(1)−C(101)
Sn(1)−O(1)
Sn(1)−O(101)
Sn(1)−X(1)
Sn(1)−X(2)
2.126(4)
2.130(5)
2.121(3)
2.109(3)
2.507(2)
2.527(2)
2.0041(17)
1.9918(17)
spectrum (Supporting Information, Figure S5), two doublets of
doublets, representing four protons each, are displaced from the
complex pattern of the other crown ether protons. The
existence of these doublets of doublets indicates diastereotopic
protons at C3/C3′ and C12/C12′. The fact that there is only
one doublet for H1 and H1′ and one multiplet for H2 and H2′
shows the equivalence of the two crown ether rings. The same
conclusion can be drawn from the 13C NMR spectrum,
containing only seven signals. Two of them are assigned to C1/
C1′ (δ 20.0) and C2/C2′ (δ 35.2), and the other five signals
represent four equivalent crown ether carbon atoms each. The
resonance for C3/C3′/C12/C12′ (δ 74.0) can be identified by
its 119Sn satellites (3J(13C−119Sn) = 98 Hz). Thus, there are two
types of protons at C3 and C12, but C3 and C12 are equal,
which proves that there are diastereotopic protons at these
carbon atoms. These findings suggest an intramolecular O→Sn
coordination, in which the four oxygen atoms O1, O1′, O5, and
O5′ have to be incorporated to the same degree. As an increase
of the coordination number in solution in comparison to the
coordination number in the solid state is unlikely, there
probably is a fast exchange of the coordinating oxygen atoms
on the NMR time scale (Scheme 2).
2.474(2)
2.480(4)
2.8068(6)
2.6152(14)
Table 4. Selected Bond Angles (deg) in Compounds 10−12
10 (X = I) 11 (X = Br) 12 (X = F)
C(1A)/C(101)−Sn(1)−C(1)
C(1)−Sn(1)−O(1A)/O(101)
C(1)−Sn(1)−O(1)
O(1A)/O(101)−Sn(1)−O(1)
C(1A)/C(101)−Sn(1)−X(1)
C(1)−Sn(1)−X(1)
O(1A)/O(101)−Sn(1)−X(1)
O(1)−Sn(1)−X(1)
X(1)−Sn(1)−X(1A)/X(2)
153.4(2)
85.56(11)
75.41(11)
88.59(11)
98.05(10)
99.34(9)
173.41(6)
87.01(6)
97.78(2)
155.6(1)
86.74(8)
75.65(8)
87.59(9)
97.07(7)
98.72(7)
171.27(4)
87.18(5)
98.83(2)
145.70(12)
87.38(11)
73.96(10)
115.14(7)
101.04(11)
103.73(11)
164.58(7)
78.68(7)
88.99(7)
The Sn−O distances in compounds 10−12 are considerably
shorter than the Sn−O distances in compounds 4−6. The
shortening of the Sn−O distances in [13]-crown-4- in
comparison to [16]-crown-5-substituted derivatives has been
noticed before16 and is probably due to steric effects combined
with the higher rigidity of the smaller ring. The longest Sn−O
distances are found in the difluorido-substituted compound 12
(2.507(2)/2.527(2) Å), and the shortest ones are found in the
diiodido-substituted derivative 10 (2.474(2) Å). The short-
ening of the Sn−O distances results in an elongation of the
corresponding Sn−X bond lengths.
Scheme 2. Behavior of the Diorganotin Dihalides 3−6 in
Solution
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Complexation Studies. (i). Diorganodiiodidostannanes
3 and 10. No effect on the 1H, 13C, and 119Sn NMR signals was
observed upon addition of 1 or 2 molar equiv of
tetraphenylphosphonium iodide (Ph4PI) to a solution of the
diorganodiidostannane 3 in CDCl3, while the addition of 2
equiv of tetraethylammonium fluoride (Et4NF·2H2O) gave the
diorganodifluorido stannane 6 within a few minutes.
Apparently, iodide anion by itself cannot change the
coordination sphere of the tin atom, which is probably due
to the strong interaction of the crown ether oxygen atoms with
the tin atom, while the presence of fluoride anion causes a
halide ion exchange instead of the formation of a stannate
complex.
3·NaI with sodium cation, while the iodide anion is kept nearby
through electrostatic interactions with the cation (Scheme 3).
Scheme 3. Reaction of Compound 3 with NaI
The 119Sn NMR spectrum of a solution of compound 3 in
CD3CN to which had been added 2 molar equiv of sodium
iodide (NaI) displayed a broad signal at δ −207 that is slightly
shifted to high frequency in comparison to that of the pure
The addition of an excess of sodium iodide to a solution of
the diorganotin diiode derivative 3 in water led to a significant
1
change of the H NMR spectrum as well. Because of the low
solubility in water, no 13C and 119Sn NMR spectra were
1
1
compound (δ −220). The H and 13C NMR spectra showed a
recorded. In the H NMR spectrum of the pure compound,
there is one doublet of doublets for the H3A/H12A protons
shifted to high frequency and the doublet of doublets assigned
to the H3B/H12B protons shifted to low frequency from the
complex pattern of the H4−H11 protons between δ 3.81 and
3.60. The center of the H2 multiplet was found at δ 2.46 and
the doublet for the H1 protons at δ 1.44 (2J(1H−119Sn) = 94
Hz). The addition of NaI caused a high-frequency shift of all
resonances. The doublets of doublets were no longer observed,
but there was only one complex pattern for all 40 CH2O
protons between δ 4.09 and 3.87. The center of the H2
multiplet shifted to δ 2.79 and the H1 doublet to δ 2.06
(2J(1H−119Sn) = 80 Hz). This shows the ability of compound 3
to complex sodium iodide in an aqueous environment.
variation of the chemical shift of all signals that was dependent
on the sodium iodide concentration, as well. The H1 doublet
2
was shifted from δ 1.91 (3J(1H−1H) = 8.4 Hz, J(1H−119Sn) =
84/87 Hz) to δ 2.10 after addition of 1 molar equiv of the salt
2
and to δ 2.39 (3J(1H−1H) = 7.3 Hz, J(1H−119Sn) = 64 Hz)
after addition of a second equivalent. The center of the H2
multiplet was shifted from δ 2.52 to 2.54 by the addition of the
first equivalent and to δ 2.66 by the addition of the second
equivalent of sodium iodide. The complex pattern for the
crown ether protons was narrowed to a smaller region. One of
the H3/H12 doublet of doublets was no longer observed but
was probably hidden under the resonances of the other crown
ether protons. The other doublet of doublets displayed a strong
variation in one of the coupling constants (from J = 6.8 Hz to J
= 1.8 Hz), whereas the other coupling constant was hardly
changed (from J = 9.3 Hz to J = 9.5 Hz). The fact that one of
the coupling constants was almost unchanged while the other
was noticeably decreased is further evidence for a geminal
coupling, as the angle between two protons at the same carbon
atom is fixed in comparison to the angle of two protons at
different carbon atoms. The 13C NMR spectra of a solution of
pure 3 in CD3CN as well as of a solution of 3 in CD3CN to
which had been added 2 molar equiv of sodium iodide
displayed seven signals. All signals were shifted by the addition
of the salt. The C1 signal suffered the biggest change, as it
moved from δ 34.8 to 40.0 and was considerably sharpened
after the addition of sodium iodide. The chemical shift for the
C2 carbon atoms remained almost unchanged (δ 38.4 with
The behavior of compound 10 toward lithium, sodium, and
cesium iodides was studied by NMR spectroscopy. No effect on
the spectra was observed after the addition of sodium and
cesium iodide, while the addition of lithium iodide resulted in a
significant change in the spectra. The 119Sn NMR resonance
shifted with broadening from δ −226 (ν1/2 = 31 Hz) to δ −216
(ν1/2 = 243 Hz). All signals in the 1H NMR spectra were shifted
to high frequency by the addition of the salt. The H3/H10
doublet of doublets was still observed, while the H3B/H10B
doublet of doublets probably coincided with the H4−H9
multiplet. The geminal coupling constant in the H3A/H10A
doublets of doublets hardly changed, while the vicinal coupling
constant decreased from 7 to 3 Hz. The H1 doublet shifted
2
from δ 1.93 to 2.25, and the J(1H−119Sn) coupling constant
decreased from 86 to 70 Hz. The most obvious changes in the
13C NMR were the high-frequency shift of the C1 signal by 5
ppm and of the C3/C10 signal by 4 ppm and the low-frequency
shift of the C4−C9 resonances. These observations indicate the
complexation of lithium cations by the crown ether moieties.
The preservation of the H3/H10 doublet of doublets and the
broadening of the 119Sn resonance suggest an equilibrium
between 10 and its complex with LiI. In the latter, the iodide
anion is probably not bound to the Lewis-acidic tin atom, as the
direction and the magnitude of the change of the chemical shift
of the 119Sn NMR resonance indicate.
2
2J(13C−119Sn) = 36 Hz to δ 39.1 with J(13C−119Sn) = 34/36
Hz). The C3/C12 signal, which was identified by its 119Sn
coupling, shifted from δ 73.9 (3J(13C−117/119Sn) = 102/106 Hz)
to δ 77.6 (3J(13C−117/119Sn) = 78/80 Hz). The other four
crown ether carbon atom signals were found between δ 71.4
and 70.0 in the pure compound and were distributed over a
wider area by the addition of the salt (between δ 71.0 and
69.6). These observations suggest an interaction of the crown
ether rings with the sodium cation. No evidence for the
nonequivalence of the crown ether rings, even after adding only
1 equiv of salt, was observed. Either there is a fast equilibrium
in which the Lewis-acidic sodium cation and the tin atom
compete for the oxygen Lewis bases or one sodium cation is
bound cooperatively by both crown ether rings. The iodide
anion probably does not bind to the tin atom. Most likely, the
diiodidodiorganostannane 3 forms the homotopic complex
(ii). Diorganodibromidostannanes 4 and 11. No effect on
1
the H and 13C NMR signals was observed after 1 or 2 molar
equiv of tetraphenylphosphonium bromide (Ph4PBr) had been
added to a solution of the diorganodibromidostannane 4 in
CDCl3, indicating the coordination sphere of the tin atom was
not affected by the bromide anion itself. Adding successively 1,
2, and 3 equiv of sodium perchlorate, (NaClO4) to a solution of
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4 in CDCl3 shows, however, that up to 2 molar equiv of
NaClO4 easily dissolved, while a third equivalent did not
dissolve at all. This indicates the simultaneous complexation of
two sodium cations by compound 4. The complexation was
(negative mode) of this solution displayed among other peaks a
mass cluster centered at m/z 765.0, which is assigned to
[11·Br]−, proving that 11 is able to complex a bromide anion.
(iii). Diorganodifluoridostannanes 6 and 12. In addition to
compounds 3 and 4, the addition of an adequate anion source
to a solution of 6 resulted in a change in the NMR spectra. The
119Sn NMR spectrum at room temperature of a solution of 6 in
CD3CN to which had been added 1 molar equiv of
Et4NF·2H2O showed no signal. After a second molar equivalent
of Et4NF·2H2O had been added, a broad resonance at δ −330
(ν1/2 = 518 Hz) was observed. The 19F NMR spectra of these
solutions displayed several signals, but no coupling to tin was
observed. The 119Sn NMR spectrum at T = 223 K (Supporting
Information, Figure S7) of a solution of 6 in CD2Cl2 to which
had been added 1 molar equiv of Et4NF·2H2O showed a
doublet of triplets resonance at δ −333 (1J(119Sn−19F) = 2656
Hz, signal a) and a triplet resonance at δ −242 (1J(119Sn−19F) =
2892 Hz, signal b, 6). The 19F NMR (Supporting Information,
Figure S6) spectrum of this solution displayed three signals at δ
−117.8 (1J(19F−117/119Sn) = 2522/2645 Hz, signal c), δ −160.5
(1J(19F−117/119Sn) = 2570/2672 Hz, signal d), and δ −164.7
(1J(19F−117/119Sn) = 2816 Hz, not resolved, signal e; 6).
Addition of a second molar equivalent of fluoride anion caused
the triplet 119Sn resonance (b) to disappear and signal (a) to
remain. The 19F NMR spectrum at T = 213 K of this solution
showed the signal (e) to disappear and the signals (c) and (d)
to remain. At this temperature, the signals (c) and (d) appeared
as a slightly broadened doublet (2J(19F−19F) = 20 Hz) and
triplet (2J(19F−19F) = 20 Hz), respectively. The signals (a), (c),
and (d) are assigned to the tetraethylammonium diorganotri-
fluoridostannate salt NEt4[6·F]. The NMR experiments
unambiguously indicate that compound 6 can complex only
one fluoride anion. Of the three fluorine atoms at the tin atom,
two are chemically and magnetically equivalent while the third
verified by H and 13C NMR spectroscopy. The H NMR
spectrum of the pure compound 4 displayed a doublet of
doublets resonance at δ 3.84 for H3A/H12A, a complex pattern
between δ 3.78 and 3.63 for H4−H11, a doublet of doublets
resonance at δ 3.46 for H3B/H12B, a multiplet centered at δ
2.57 for H2, and a doublet for H1 at δ 1.65 (2J(1H−119Sn) = 93
Hz). The variation of the 1H NMR spectrum after the addition
of the salt was manifested by (i) the merging of the doublets of
doublets for the H3/H12 protons and the multiplet for the
H4−H11 protons into one multiplet between δ 3.82 and 3.53
and (ii) the transformation of the H1 doublet into a broad
singlet at δ 1.79 (2J(1H−117/119Sn) = 80 Hz). In the 13C NMR
spectrum the most obvious change was the disappearance of
the C1 signal after the addition of the salt.
1
1
The addition of 1 equiv of NaBr to a solution of 4 in CDCl3
resulted in neither the dissolution of the salt nor in a change in
the NMR spectra, while the same experiment in both CD3CN
and CD3OD led to the dissolution of the salt and a change of
the 1H and 119Sn spectra. The 1H NMR spectrum of a solution
of 4 in CD3CN to which had been added NaBr was quite
similar to that of a solution of 4 to which had been added
NaClO4. This showed the complexation of sodium cations by
the crown ether moieties of 4. The 119Sn NMR resonance was
shifted from δ −142 to −178. This low-frequency shift is
probably due to the coordination of an additional bromide
anion to the Lewis-acidic tin atom and suggests that compound
4 is able to ditopically complex NaBr in acetonitrile (Scheme
4).
Scheme 4. Reaction of Compound 4 with NaBr
1
atom is different (Chart 2). The H and 13C NMR spectra of
Chart 2
Remarkably, the solubility of compound 4 in CD3CN and
even more so in CD3OD was significantly increased by the
addition of the salt. Due to the low solubility no 119Sn NMR
signal was observed for 4 in CD3OD. However, after NaBr had
been added to the solution, the 119Sn NMR spectrum showed a
these solutions at room temperature showed one set of signals
for the crown ether moieties, revealing that the latter are
equivalent. Apparently, the diorganotrifluorido stannate anion
[6·F]− is kinetically inert on the 19F and 119Sn NMR time scales
at low temperature but kinetically labile at room temperature
1
resonance at δ −115. As the changes of the H NMR spectra
1
after the addition of the salt are comparable to those of the
spectra in CD3CN, it is concluded that compound 4 can
complex NaBr in methanol as well.
on these and the H and 13C NMR time scales.
No effect on the NMR spectra was observed after the
addition of LiF and NaF to a solution of 6 in CDCl3 or
CD3CN. This showed that the complexation ability of
compound 6 is not high enough to overcome the lattice
energy of lithium and sodium fluoride in organic solvents.
Adding sodium fluoride to a solution of 6 in water resulted in
the salting out of most of the receptor. The 1H NMR spectra of
a solution of pure 6 in D2O and a solution of 6 in D2O to which
had been added NaF differed slightly. It could not be clarified if
these changes in the spectra and the decrease of solubility were
due to the complexation of the salt or to an increase of the
capacity of the solvent, which was caused by the addition of the
salt.
Attempts at complexing, with both crown ether moieties, one
cation that prefers a higher coordination number were not
successful. The addition of neither LaBr3·H2O nor MgBr2 to a
solution of 4 in CD3CN caused dissolution of the salt or a
significant change of the NMR spectra in comparison to those
of the pure compound.
Comparison of the NMR spectra of a solution of pure 11 in
CD3CN and a solution of 11 to which had been added LiBr
showed that 11 can complex LiBr. The variations in the spectra
were quite similar to those observed in the spectra of 4 and of 4
to which had been added NaBr. The ESI mass spectrum
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The 19F and 119Sn NMR spectra of a solution of 6 in CD3CN
or CD3OD to which had been added CsF displayed no signals
at room temperature which could be assigned to 6 or a complex
the corresponding diorganotrifluoridostannate salt takes place.
For future investigations the presence of hydrogen bonds
between the crown ether oxygen atoms and water must also be
taken into account. These might compete with the metal
cations for interaction with the crown ether.
1
of 6. The H and 13C NMR spectra were slightly changed by
the addition of the salt. This suggests equilibrium, which is fast
on the NMR time scale at room temperature. The 119Sn NMR
spectrum at 213 K displayed one triplet at δ −255 and one very
broad resonance at δ −337. The 19F NMR spectrum at the
same temperature showed several signals. None of them
matches with pure 6. These observations point at an interaction
of 6 with CsF, but 213 K is not cold enough to freeze the
equilibrium and no statement can be made about this
interaction.
EXPERIMENTAL SECTION
■
General Methods. All solvents were purified by distillation under
an argon atmosphere from the appropriate drying agents. The
hydrostannation was carried out under an argon atmosphere as well.
15-Methylene-1,4,7,10,13-pentaoxacyclohexadecane, iodido-
(1,4,7,10,13-pentaoxahexadec-15-ylmethyl)diphenylstannane,
(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)triphenylstannane, and 12-
methylene-1,4,7,10-tetraoxacyclotridecan were synthesized as de-
scribed in the literature. The NMR experiments were carried out on
a Bruker DRX 400, a Bruker DPX 300, or a Varian Mercury 200
spectrometer. NMR experiments were carried out at ambient
temperature unless otherwise stated. Chemical shifts (δ) are given in
ppm and are referenced to the solvent peaks with the values calibrated
against tetramethylsilane (1H, 13C), CFCl3 (19F), and tetramethyl-
stannane (119Sn).
Adding 2 equiv of silver fluoride to a solution of 6 in CD3CN
resulted in the disappearance of the 119Sn NMR signal. The 19
F
NMR spectrum of this solution displayed one rather broad
resonance at δ −138 (ν1/2 = 1200 Hz) and one sharp resonance
at δ −130. The latter was assigned to “free” fluoride anion and
1
the former with caution to a complex of 6 with AgF. The H
and 13C NMR spectra of the solutions of 6 to which had been
added AgF also differed from those of the pure compound. The
most obvious changes were the shifting of the C1 signal by
almost 3 ppm from δ 20.8 to 23.7 and the overlapping of two of
the crown ether signals after the addition of the salt. These
observations suggest a complexation of silver fluoride by
compound 6. This finding is supported by the fact that the
silver ion containing solution did not darken, even after several
weeks of exposure to light.
The partial assignments of the 13C NMR data for the crown ether
moieties refer to the numbering schemes in Chart 3.
Chart 3
The behavior of compound 12 toward lithium, cesium, and
silver fluorides was studied by NMR spectroscopy. No effect on
the NMR spectra was observed after the addition of lithium
fluoride to a solution of 12 in CD3CN. The addition of cesium
fluoride to a solution of 12 in CDCl3 resulted in the broadening
Synthesis of Hydrido(1,4,7,10,13-pentaoxacyclohexadec-
15-ylmethyl)diphenylstannane, Ph2HSnCH2-[16]-crown-5 (1).
Iodido(1,4,7,10,13-pentaoxacyclohexadec-15-ylmethyl)-diphenylstan-
nane1 (2.00 g, 3.09 mmol) was added to an ice-cooled slurry of LiAlH4
(0.50 g, 13.16 mmol) in diethyl ether (100 mL). After the reaction
mixture had been stirred for 15 min at 0 °C and a further 3 h at room
temperature, the reaction was quenched by adding 30 mL of degassed
potassium sodium tartrate solution. After the phases were separated,
the organic phase was washed with degassed potassium sodium tartrate
solution (4 × 100 mL), dried over magnesium sulfate, and filtered.
Evaporating the solvent in vacuo yielded 1.00 g (1.92 mmol, 62%) of 1
as a colorless oil. Crude 1 was used in the next step without further
1
of the H1 and H2 signals in the H NMR spectrum and the
disappearance of the 19F NMR signal. The effect of the addition
of silver fluoride was comparable to the addition of silver
fluoride to a solution of 6, which suggests that 12 is able to
build a complex with silver fluoride.
Remarkably, compounds 6 and 12 do not interact with
lithium or sodium fluoride, although they contain crown ether
moieties designed for the complexation of lithium and sodium
cations, respectively, but they do interact with silver fluoride.
The lattice energies of these three fluoride salts are in the same
region (LiF, 1037 kJ/mol; NaF, 926 kJ/mol; AgF, 969 kJ/mol);
therefore, this effect is probably due to the better solubility of
silver fluoride in comparison to the alkali-metal fluorides.
1
purification. H NMR (300.13 MHz, C6D6, 293 K): δ 7.78−7.58 (m,
3
4Ho, J(1H−117/119Sn) = 48 Hz), 7.35−7.17 (m, 6Hm/p), 6.56 (s, 1H,
Sn-H), 3.76−3.71 (m, 2H, H3A/H12A), 3.54−3.25 (m, 18H, H4−
3
H11+ H3B/H12B), 2.45 (m, 1H, H2), 1.24 (dd, 2H, H1, J(1H−1H)
= 7 Hz, 2J(1H−1H) = 2 Hz, 2J(1H−117/119Sn) = 60 Hz). 13C{1H} NMR
(100.63 MHz, C6D6) δ: 141.25 (Ci, 1J(13C−117/119Sn) = 463/485 Hz),
137.85 (Co, 2J(13C−117/119Sn) = 35 Hz), 128.96 (Cp, 4J(13C−117/119Sn)
CONCLUSION
■
A series of bis(crown ether)-substituted organotin dihalides was
synthesized and completely characterized, and their ability in
the ditopic complexation of alkali-metal salts was investigated.
In the solid state as well as in solution in all compounds both
crown ether moieties coordinate the tin atoms via intra-
molecular O→Sn interactions. By the addition of sodium halide
salts, only one of these two O→Sn interactions is broken in
favor of forming mono- and ditopic complexes 3·NaI and
4·NaBr, respectively. There was no evidence for the existence in
solution or in the solid state of the complexes 3·2NaI and
4·2NaBr. On the other hand, the diorganotin difluorides 6 and
12 are not able to compensate for the high lattice energy of
both lithium and sodium fluoride by formation of the
corresponding ditopic complexes. Nevertheless, rupture of the
O→Sn coordination in compound 6 by Et4NF·2H2O to give
3
= 11 Hz, 128.93 (Cm, J(13C−117/119Sn) = 47 Hz), 75.07 (C3/C12,
3J(13C−117/119Sn) = 50 Hz, 71.82, 71.33, 71.31, 70.48, 38.33 (C2,
1
2J(13C−117/119Sn) = 24 Hz, 11.70 (C1, J(13C−117/119Sn) = 414/433
Hz). 119Sn{1H} NMR (111.92 MHz, C6D6, 293 K): δ −147. 119Sn
1
NMR (111.92 MHz, C6D6): δ −147 (d, J(119Sn−1H) = 1903 Hz).
Anal. Calcd for C24H34O5Sn (521.23): C, 55.30; H, 6.57. Found: C,
54.3; H, 6.65.
Synthesis of Bis(1,4,7,10,13-pentaoxacyclohexadec-15-
ylmethyl)diphenylstannane, Ph2SnCH2-[16]-crown-5 (2). Com-
pound 1 (1.00 g, 1.92 mmol), 15-methylene-1,4,7,10,13-pentaoxacy-
clohexadecane (0.50 g, 2.01 mmol), and a small quantity of AIBN
(0.05 g) were mixed and stirred for 15 h at 70 °C. After cooling of the
mixture to room temperature, addition of 70 mL of CH2Cl2, filtration
through Celite, and evaporation of the solvent in vacuo, 1.49 g (1.91
mmol, 99%) of 2 was obtained as a colorless oil. Crude 2 was used in
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1
the next step without further purification. H NMR (300.13 MHz,
CDCl3, 293 K): δ 7.56−7.38 (m, 4Ho), 7.29−7.19 (m, 6Hm/p), 3.69−
3.20 (m, 40H, H3−H12), 2.29−2.16 (m, 2H, H2), 1.19 (d, 4H, H1,
3J(1H−1H) = 7 Hz, 2J(1H−117/119Sn) = 57 Hz). 13C{1H} NMR
(br s, C1). 119Sn{1H} NMR (111.92 MHz, CDCl3): δ −137.
119Sn{1H} NMR (111.92 MHz, CD3CN): δ −142. 119Sn{1H} NMR
(111.92 MHz, CD3OD): no signal observed. Anal. Calcd for
C24H46Br2O10Sn (773.13): C, 37.28; H, 6.00. Found: C, 37.25; H,
5.95. Mp: 123 °C.
(100.63 MHz, CDCl3): δ 142.51, 136.57, 127.92, 113.43, 74.26
(3J(13C−117/119Sn) 47 Hz, C3/C12), 70.81, 70.66, 70.42, 69.70, 37.12
(C2), 11.54 (C1). 119Sn{1H} NMR (111.92 MHz, CDCl3, 293 K): δ
−82. Anal. Calcd for C36H56O10Sn·0.5 CH2Cl2 (767.53): C, 54.12; H,
7.09. Found: C, 54.20; H, 7.35.
Synthesis of Dichloridobis(1,4,7,10,13-pentaoxacyclohexa-
dec-15-ylmethyl)stannane, Cl2Sn(CH2-[16]-crown-5)2 (5). A
solution of iodine chloride (0.42 g, 2.60 mmol) in dichloromethane
(20 mL) was added dropwise to an ice-cooled solution of 2 (1.00 g,
1.30 mmol) in dichloromethane (30 mL). The reaction mixture was
warmed to room temperature and was stirred for a further 15 h. All
volatile material was evaporated in vacuo. The residue was extracted
with hot hexane, and the extract was dried. Recrystallization of the
residue afforded 0.05 g (0.072 mmol, 0.6%) of compound 5 as
colorless crystals. These crystals were suitable for single-crystal X-ray
Synthesis of Diiodidobis(1,4,7,10,13-pentaoxacyclohexa-
dec-15-ylmethyl)stannane, I2SnCH2-[16]-crown-5 (3). Over a
period of 12 h, iodine (0.97 g, 3.84 mmol) was added in small portions
to an ice-cooled, stirred solution of 2 (1.49 g, 1.91 mmol) in
dichloromethane (10 mL). After complete addition of the iodine, the
reaction mixture was warmed to room temperature and stirred for a
further 30 h. Evaporation of the solvent and most of the formed
iodobenzene in vacuo (10−3 mbar) gave a dark red, viscous oil.
Recrystallization of this oil from ethanol allowed separation of
diiodido(1,4,7,10,13-pentaoxacyclohexadec-15-ylmethyl)-
phenylstannane. Removal of the remaining iodobenzene in vacuo
afforded 1.23 g (1.42 mmol, 74%) of 3 as a dark red, viscous oil, which
solidified upon standing for several days. 1H NMR (300.13 MHz,
1
diffraction analysis. H NMR (300.13 MHz, CDCl3): δ 3.81 (dd, 4H,
2
3
H3A/H12A, J(1H−1H) = 9 Hz, J(1H−1H) = 7 Hz), 3.76−3.55 (m,
34H, H4−H11), 3.43 (dd, 4H, H3B/H12B, 2J(1H−1H) = 9 Hz,
3J(1H−1H) = 7 Hz), 2.66−2.35 (m, 2H, H2, J(1H−117/119Sn) = 54
3
Hz), 1.43 (d, 4H, H1, J(1H−1H) = 8 Hz, 2J(1H−117/119Sn) = 96/100
3
Hz). 13C NMR (100.63 MHz, CDCl3): δ 73.97 (C3/C12,
3J(13C−117/119Sn) = 104 Hz), 70.73, 70.32, 70.27, 69.89, 36.02 (C2,
2J(13C−117/119Sn) = 32 Hz), 28.77 (C1). 119Sn{1H} NMR (111.92
CDCl3, 293 K): δ 3.79 (dd, 4H, H3A/H12A, J(1H−1H) = 9.2 Hz,
2
3J(1H−1H) = 7.0 Hz), 3.72−3.55 (m, 32H, H4−H11), 3.41 (dd, 4H,
MHz, CDCl3): δ −112. Anal. Calcd for C24H46Cl2O10Sn (684.23): C,
42.13; H, 6.78. Found: C, 40.85; H, 6.25. Mp: 136 °C.
H3B/H12B, J(1H−1H) = 9.2 Hz, J(1H−1H) = 7.7 Hz), 2.69−2.37
(m, 2H, H2), 1.86 (d, 4H, H1, 3J(1H−1H) = 8.6 Hz, 2J(1H−117/119Sn)
= 85 Hz). 13C{1H} NMR (75.48 MHz, CDCl3, 293 K): δ 73.3 (C3/
2
3
Synthesis of Difluoridobis(1,4,7,10,13-pentaoxacyclohexa-
dec-15-ylmethyl)stannane, F2Sn(CH2-[16]-crown-5)2 (6). Silver
fluoride (AgF; 0.22 g, 1.71 mmol), was added to a solution of 0.74 g
(0.86 mmol) of 3 in 10 mL of dichloromethane. The resulting mixture
was stirred at room temperature in the dark for 8 h. Removal of the
formed silver iodide by filtration and evaporation of the solvent in
vacuo afforded 0.55 g (0.84 mmol, 98%) of 6 as a slightly yellow oil,
which became solid upon standing at room temperature. Single
crystals of 6 suitable for single-crystal X-ray diffraction analysis were
obtained by slow evaporation of a solution of 6 in CH2Cl2/hexane. 1H
NMR (300.13 MHz, CDCl3, 293 K): δ 3.77−3.53 (m, 36H, H4−
H11+H3A/H12A), 3.44−3.39 (dd, 4H, H3B/H12B), 2.39 (m, 2H,
H2), 1.11 (d, 4H, H1, 3J(1H−1H) = 7.7 Hz, 2J(1H−119Sn) = 101 Hz).
13C{1H} NMR (100.63 MHz, CDCl3, 293 K): δ 74.0 (C3/C12,
C12, J(13C−117/119Sn) = 98 Hz), 70.7, 70.4, 70.3, 70.2, 37.4 (C2,
3
2J(13C−117/119Sn) = 37 Hz), 33.0 (C1). 119Sn{1H} NMR (111.92
1
MHz, CDCl3, 293 K): δ −227. H NMR (300.13 MHz, CD3CN, 293
K): δ 3.80 (dd, 4H, H3A/H12A, J(1H−1H) = 9.3 Hz, J(1H−1H) =
2
3
6.8 Hz), 3.73−3.47 (m, 32H, H4−H11), 3.39 (dd, 4H, H3B/H12B,
2J(1H−1H) = 9.1 Hz, J(1H−1H) = 7.7 Hz), 2.55−2.45 (m, 2H, H2),
3
1.91 (d, 4H, H1, J(1H−1H) = 8.4 Hz, J(1H−117/119Sn) = 85 Hz).
13C{1H} NMR (75.48 MHz, CD3CN, 293 K): δ 72.9 (C3/C12,
3J(13C−117/119Sn) = 102 Hz/106 Hz), 70.4, 70.2, 70.1, 70.0, 37.4 (C2,
2J(13C−117/119Sn) = 38 Hz), 33.8 (br s, C1). 119Sn{1H} NMR (111.92
MHz, CD3CN, 293 K): δ −220. 1H NMR (300.13 MHz, D2O): δ 3.76
(dd, 4H, H3A/H12A, 2J(1H−1H) = 10 Hz, 3J(1H−1H) = 7 Hz), 3.81−
3.60 (m, 32H, H4−H11), 3.51 (dd, 4H, H3B/H12B, 2J(1H−1H) = 10
3
2
3J(13C−117/119Sn) = 95 Hz), 70.6 (J(13C−117/119Sn) = 29.2 Hz), 70.3,
70.2, 69.7 (J(13C−117/119Sn) = 130.2 Hz), 35.3 (C2), 20.0 (C1). 19F
NMR (282.38 MHz, CDCl3, 293 K): δ −167.8 (s, 1J(19F−117/119Sn) =
2760/2889 Hz). 119Sn{1H} NMR (111.92 MHz, CDCl3, 293 K): δ
−236 (t, 1J(119Sn−19F) = 2889 Hz). 1H NMR (300.13 MHz, CD3CN,
293 K): δ 3.75−3.51 (m, 36H, H4−H11+H3A/H12A), 3.41−3.36
(dd, 4H, H3B/H12B), 2.32 (m, 2H, H2), 1.05 (d, 4H, H1, 3J(1H−1H)
= 8.1 Hz, 2J(1H−117/119Sn) = 101.4 Hz). 13C{1H} NMR (100.63 MHz,
CD3CN, 293 K): δ 74.7 (C3/C12, J(13C−117/119Sn) = 99.1 Hz), 71.5,
Hz, J(1H−1H) = 7 Hz), 2.53−2.39 (m, 2H, H2, J(1H−117/119Sn) =
3
3
75 Hz), 1.44 (d, 4H, H1, J(1H−1H) = 8 Hz, J(1H−117/119Sn) = 93
Hz). Anal. Calcd for C24H46I2O10Sn (867.14): C, 33.24; H, 5.35.
Found: C, 33.45; H, 5.40. Mp: 115 °C.
3
2
Synthesis of Dibromidobis(1,4,7,10,13-pentaoxacyclohexa-
dec-15-ylmethyl)stannane, Br2Sn(CH2-[16]-crown-5)2 (4). A
solution of elemental bromine (0.91 g, 5.71 mmol) in dichloro-
methane (30 mL) was added drop by drop to an ice-cooled solution of
2 (2.19 g, 2.86 mmol) in dichloromethane (100 mL). The reaction
mixture was warmed to room temperature and stirred for a further 15
h. All volatile material was removed in vacuo. The residue was
extracted with toluene, and the extract was dried. Recrystallization of
the residue in ethanol afforded 2.16 g (2.80 mmol, 98%) of compound
4 as a white, microcrystalline solid. Crystals suitable for single-crystal
X-ray diffraction analysis were obtained by slow evaporation of a
toluene solution of the compound. 1H NMR (300.13 MHz, CDCl3): δ
2
71.1, 71.0, 70.7, 36.4 (C2, J(13C−117/119Sn) = 27.2 Hz), 20.8 (C1).
19F NMR (282.38 MHz, CD3CN, 293 K): δ −167.4 (s,
1J(19F−117/119Sn) = 2760/2887 Hz). 119Sn{1H} NMR (111.92 MHz,
1
1
CD3CN, 293 K): δ −236 (t, J(119Sn−19F) = 2887 Hz). H NMR
(300.13 MHz, D2O, 293 K): δ 3.85−3.58 (m, 36H, H4−H11+H3A/
H12A), 3.50−3.42 (dd, 4H, H3B/H12B), 2.42 (m, 2H, H2), 1.19 (d,
3
2
4H, H1, J(1H−1H) = 7.3 Hz, J(1H−117/119Sn) = 97 Hz). 19F NMR
(282.37 MHz, CD2Cl2, 293 K): δ −167.7 (s,1J(19F−117/119Sn) = 2763/
2879 Hz). 119Sn{1H} NMR (111.92 MHz, CD2Cl2, 293 K): δ −234 (t,
1J(119Sn−19F) = 2878 Hz). 19F NMR (282.37 MHz, CD2Cl2, −49 °C):
3.84 (dd, 4H, H3A/H12A, J(1H−1H) = 7 Hz, J(1H−1H) = 9 Hz),
3.78−3.63 (m, 32H, H4−H11), 3.46 (dd, 4H, H3B/H12B, 3J(1H−1H)
= 7.32 Hz, 2J(1H−1H) = 8.78 Hz), 2.57 (m, 2H, H2, 3J(1H−117/119Sn)
= 75 Hz), 1.65 (d, 4H, H1, 3J(1H−1H) = 8.42 Hz, 2J(1H−117/119Sn) =
93 Hz). 1H NMR (300.13 MHz, CD3CN): δ 3.82−3.77 (m, 4H,
H3A/H12A), 3.74−3.49 (m, 32 H, H4−H11), 3.42−3.36 (m, 4H,
H3B/H12B), 2.48 (m, 2H, H2), 1.61 (d, 4H, H1, 3J(1H−1H) = 8 Hz,
3
2
δ −164.8 (s, J(19F−117/119Sn) = 2811 Hz), 119Sn{1H} NMR (111.92
1
MHz, CD2Cl2, −49 °C): δ −242 (t, J(119Sn−19F) = 2884 Hz). Anal.
1
Calcd for C24H46F2O10Sn (651.32): C, 44.26; H 7.12. Found: C, 44.3;
H 6.9, Mp: 110 °C.
Synthesis of Bromido(1,4,7,10-tetraoxacyclotridec-12-
ylmethyl)diphenylstannane, BrPh2SnCH2-[13]-crown-4 (7). A
solution of elemental bromine (2.20 g, 13.79 mmol) in dichloro-
methane (85 mL) was added dropwise to a solution of (1,4,7,10-
tetraoxacyclotridec-12-ylmethyl)triphenylstannane (7.63 g, 13.79
mmol) in dichloromethane (160 mL) at −55 °C. The reaction
mixture was warmed to room temperature and stirred for a further 15
2J(1H−117/119Sn) = 83/86 Hz). H NMR (300.13 MHz, CD3OD): δ
1
2.60−2.54 (m, 4H, H3A/H12A), 2.52−2.30 (m, 32 H, H4−H11),
2.21−2.16 (m, 4H, H3B/H12B), 1.35−1.25 (m, 2H, H2), 0.35 (d, 4H,
H1, J(1H−1H) = 8 Hz, J(1H−117/119Sn) = 94 Hz).13C{1H} NMR
(100.63 MHz, CDCl3): δ 73.45 (C3/C12), 70.36 (C4/C11,
J(13C−117/119Sn) = 48 Hz), 69.95, 69.91, 69.69, 36.18 (C2), 31.26
3
2
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h. All volatile material was removed in vacuo (10−3 mbar).
Recrystallization of the residue in ethanol afforded 6.90 g (12.41
mmol, 90%) of bromido(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)-
H1, 3J(1H−1H) = 7 Hz, 2J(1H−117/119Sn) = 78/84 Hz). 1H NMR (400
3
MHz, CD3CN): δ 3.87 (dd, 4H, H3A/H10A, J(1H−1H) = 7 Hz,
2J(1H−1H) = 9 Hz), 3.54−3.72 (m, 24H, H4−H9), 3.51 (dd, 4H,
1
3
2
H3B/H10B, J(1H−1H) = 6 Hz, J(1H−1H) = 9 Hz), 2.51−2.63 (m,
2H, H2), 1.93 (d, 4H, H1, 3J(1H−1H) = 7 Hz, 2J(1H−117/119Sn) = 83/
87 Hz). 13C{1H} NMR (125.68 MHz, CDCl3): δ 71.00 (C3/C10,
3J(13C−117/119Sn) = 70/75 Hz), 70.36, 70.10, 69.52, 37.33 (C2), 31.33
(br s, C1). 13C{1H} NMR (100.63 MHz, CD3CN): δ 72.03 (C3/C10,
3J(13C−117/119Sn) = 80/84 Hz), 71.25 (C4/C9, 2/5J(13C−117/119Sn) =
diphenylstannane (7) as a colorless solid. H NMR (300.13 MHz,
CDCl3): δ 7.79−7.76 (m, 4Ho, 3J(1H−117/119Sn) = 63 Hz), 7.46−7.36
(m, 6Hm/p), 3.78−3.73 (m, 2H), 3.62−3.34 (m, 14H), 2.74−2.62 (m,
1H, H2, 3J(1H−117/119Sn) = 156/162 Hz), 1.76 (d, 2H, H1,
2
3J(1H−1H) = 6 Hz, J(1H−117/119Sn) = 75/77 Hz). 13C{1H}-NMR
1
(75.47 MHz, CDCl3): δ 140.74 (Ci, J(13C−117/119Sn) = 631 Hz),
135.76 (Co, 2J(13C−117/119Sn) = 47/50 Hz), 129.39 (Cp,
2
130/134 Hz), 70.91, 70.42, 38.16 (C2, J(13C−117/119Sn) = 40 Hz),
3
4J(13C−117/119Sn) = 14 Hz), 129.59 (Cm, J(13C−117/119Sn) = 62/65
33.78 (br s, C1). 119Sn{1H} NMR (111.92 MHz, CDCl3): δ −227.
3
Hz), 71.14 (C3/C10, J(13C−117/119Sn) = 38 Hz), 70.02, 69.54 (C4/
119Sn{1H} NMR (111.92 MHz, CD3CN): δ −226. Anal. Calcd for
2
C9, J(13C−117/119Sn) = 39 Hz), 69.17, 36.57 (C2, J(13C−117/119Sn) =
C20H38I2O8Sn (779.03): C, 30.84; H, 4.92. Found: C, 30.90; H, 4.50.
Mp: 146 °C.
29 Hz), 18.38 (C1, 1J(13C−117/119Sn) = 499/521 Hz). 119Sn{1H}
NMR (111.92, CDCl3): δ −96. Anal. Calcd for C22H29BrO4Sn
(556.08): C, 47.52; H, 5.26. Found: C, 47.15; H, 5.10. Mp: 137.1 °C.
Synthesis of Hydrido(1,4,7,10-tetraoxacyclotridec-12-
ylmethyl)diphenylstannane, HPh2SnCH2-[13]-crown-4 (8). Bro-
midotriorganostannane 7 (4.00 g, 7.19 mmol) was added to an ice-
cooled suspension of LiAlH4 (1.00 g, 26.32 mmol) in diethyl ether
(125 mL). The reaction mixture was warmed to room temperature
within 6 h. To destroy the excess LiAlH4 and to remove the aluminum
salts, a degassed, aqueous solution of potassium sodium tartrate was
added until hydrogen formation ceased. Afterward, the organic phase
was washed with potassium sodium tartrate solution several times. The
organic phase was separated, dried with magnesium sulfate, and
filtered. Evaporation of the solvent provided 3.09 g (90%) of
hydrido(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)diphenylstannane
(8) as a colorless oil, which was contaminated with the crown ether
substituted distannane ([13]-crown-4-CH2(Ph)2Sn)2. The crude
Synthesis of Dibromidobis(1,4,7,10-tetraoxacyclotridec-12-
ylmethyl)stannane, Br2Sn(CH2-[13]-crown-4)2 (11). A solution of
elemental bromine (1.62 g, 10.1 mmol) in dichloromethane (30 mL)
was added dropwise to an ice-cooled solution of 9 (3.45 g, 5.1 mmol)
in dichloromethane (70 mL). The reaction mixture was warmed to
room temperature and stirred for a further 15 h. All volatile material
was removed from the reaction mixture. Recrystallization in ethanol
afforded 1.53 g (2.24 mmol, 44%) of 11 as a colorless, amorphous
solid. Crystals suitable for single-crystal X-ray diffraction analysis were
obtained by slow evaporation of a dichloromethane solution of
compound 11. 1H NMR (300.13 MHz, CDCl3): δ 3.81 (dd, 4H,
3
2
H3A/H10A, J(1H−1H) = 7 Hz, J(1H−1H) = 9 Hz), 3.75−3.56 (m,
28H, H3B/H10B+H4−H9), 2.70−2.57 (m, 2H, H2, 3J(1H−117/119Sn)
= 169/180 Hz), 1.72 (d, 4H, H1, 3J(1H−1H) = 6 Hz, 2J(1H−117/119Sn)
1
= 88/90 Hz). H NMR (300.13 MHz, CD3CN): δ 3.80 (dd, 4H,
3
2
H3A/H10A, J(1H−1H) = 8 Hz, J(1H−1H) = 9 Hz), 3.73−3.50 (m,
24H, H4−H9), 3.54 (dd, 4H, H3B/H10B, 3J(1H−1H) = 6 Hz,
1
product was used in the next step without further purification. H
2J(1H−1H) = 9 Hz), 2.66−2.53 (m, 2H, H2, J(1H−117/119Sn) = 163
3
NMR (300.13 MHz, C6D6): δ 7.61−7.58 (m, 4Ho, 2J(1H−117/119Sn) =
50 Hz), 7.22−7.09 (m, 6Hm/p), 6.48 (t, 1H, Sn−H, 3J(1H−1H) = 2 Hz,
1J(1H−117/119Sn) = 1831/1921 Hz), 3.65 (dd, 2H, H3A/H10A,
Hz), 1.65 (d, 4H, H1, J(1H−1H) = 7 Hz, J(1H−117/119Sn) = 90/94
3
2
1
Hz). H NMR (400.13 MHz, CD3OD): δ 3.84 (dd, 4H, H3A/H10A,
3J(1H−1H) = 7 Hz, J(1H−1H) = 9 Hz), 3.79−3.61 (m, 28H, H3B/
2
2
3J(1H−1H) = 6 Hz, J(1H−1H) = 9 Hz), 3.44−3.21 (m, 18H, H3B/
H10B+H4−H9), 2.68−2.62 (m, 2H, H2, 3J(1H−117/119Sn) = 170/178
H10B + H4−H9), 2.41−2.32 (m, 1H, H2), 1.14 (dd, 2H, H1,
Hz), 1.71 (d, 4H, H1, J(1H−1H) = 7 Hz, J(1H−117/119Sn) = 89/93
Hz). 13C{1H} NMR (100.63 MHz, CD3OD): δ 72.56, 71.60, 71.37,
70.83, 37.89 (C2), no C1 signal was observed. 119Sn{1H} NMR
(111.92 MHz, CDCl3): δ −135. 119Sn{1H} NMR (111.92 MHz,
CD3CN): δ −147. Anal. Calcd for C20H38Br2O8Sn (685.03): C, 35.07;
H, 5.59. Found: C, 35.14; H, 5.35. Mp: 129 C.
3
2
3
2
3J(1H−1H) = 2 Hz, J(1H−1H) = 7 Hz, J(1H−117/119Sn) = 60 Hz).
119Sn{1H} NMR (111.92 MHz, C6D6): δ −147. Anal. Calcd for
C22H30O4Sn (477.18): C, 55.37; H, 6.54. Found: C, 55.10; H, 6.70.
Synthesis of Bis(1,4,7,10-tetraoxacyclotridec-12-ylmethyl)-
diphenylstannane, Ph2Sn(CH2-[13]-crown-4)2 (9). Triorganohy-
dridostannane 8 (3.09 g, 6.47 mmol), 12-methylene-1,4,7,10-
tetraoxacyclotridecane (1.31 g, 6.47 mmol), and AIBN (50 mg)
were mixed and stirred for 15 h at 70 °C. The reaction mixture was
cooled to room temperature and dissolved in dichloromethane, and
the solution was filtered through Celite. Evaporation of the solvent
afforded 2.98 g of a mixture of Ph2Sn(CH2-[13]-crown-4)2 (9) and the
crown ether substituted distannane ([13]-crown-4-CH2(Ph)2Sn)2.
The crude product was used in the next steps without further
Synthesis of Difluorido(1,4,7,10-tetraoxacyclotridec-12-
ylmethyl)diphenylstannane, F2Sn(CH2-[13]-crown-4)2 (12). Sil-
ver fluoride (59 mg, 0.47 mmol) was added to a solution of 10 (181
mg, 0.23 mmol) in dichloromethane. The reaction mixture was stirred
for 5 h in the dark. Afterward, the formed silver iodide was removed by
filtration. The evaporation of the solvent gave 130 mg (0.23 mmol) of
12 as a colorless amorphous solid. Crystals suitable for single-crystal X-
ray diffraction analysis were obtained by slow evaporation of a
1
purification. H NMR (300.13 MHz, CDCl3): δ 7.49−7.48 (m, 4Ho),
1
dichloromethane solution of compound 12. H NMR (300.13 MHz,
7.26−7.17 (m, 6Hm/p), 3.67−3.19 (m, 40H, H3−H10), 2.19−2.08 (m,
3
2
CDCl3): δ 3.75−3.53 (m, 32H, H3−H10), 2.62−2.47 (m, 2H, H2,
2H, H2), 1.24 (d, 4H, H1, J(1H−1H) = 7 Hz, J(1H−117/119Sn) = 57
Hz). 119Sn{1H} NMR (111.92 MHz, CDCl3): δ −78 (1J(119Sn−13C) =
382/450 Hz). Anal. Calcd for C32H48O8Sn (679.43): C, 56.47; H,
7.02. Found: C, 56.10; H, 6.75.
3
3J(1H−117/119Sn) = 198 Hz), 1.26 (d, 4H, H1, J(1H−1H) = 6 Hz,
2J(1H−117/119Sn) = 97 Hz). 1H NMR (300.13 MHz, CD3CN): δ
3.72−3.41 (m, 32H, H3−H10), 2.53−2.45 (m, 2H, H2,
3J(1H−117/119Sn)
= 184/193 Hz), 1.19 (br s, 4H, H1,
Synthesis of Diiodidobis(1,4,7,10-tetraoxacyclotridec-12-
ylmethyl)stannane, I2Sn(CH2-[13]-crown-4)2 (10). Elemental
iodine (2.20 g, 8.7 mmol) was added in small portions to a cooled
solution of 9 (2.95 g, 4.3 mmol) in dichloromethane (50 mL).
Afterward, the reaction mixture was warmed to room temperature and
stirred for a further 15 h. All volatile material was removed in vacuo.
Recrystallization in ethanol afforded 1.76 g (2.3 mmol, 52%) of
compound 10 as a light yellow, microcrystalline solid. Crystals suitable
for single-crystal X-ray diffraction analysis were obtained by slow
evaporation of a solution of the compound in dichloromethane/
hexane. 1H NMR (499.79 MHz, CDCl3): δ 3.87 (dd, 4H, H3A/H10A,
2J(1H−117/119Sn) = 96 Hz). 13C{1H} NMR (75.47 MHz, CD3CN):
δ 72.04 (C3/C10, 3J(13C−117/119Sn) = 59/61 Hz), 70.88, 70.61, 70.09,
2
36.23 (C2, J(13C−117/119Sn) = 32 Hz), 20.47 (br s, C1). 19F NMR
(282.40 MHz, CDCl3): δ −168 (1J(19F−117/119Sn) = 2710/2831 Hz).
19F NMR (282.40 MHz, CD3CN): δ −164 (1J(19F−117/119Sn) = 2800
Hz). 119Sn{1H} NMR (111.92 MHz, CDCl3): δ −235 (1J(119Sn−19F)
= 2834 Hz). 119Sn{1H} NMR (111.92 MHz, CD3CN): δ −235
(1J(119Sn−19F) = 2816 Hz). Anal. Calcd for C20H38F2O8Sn (563.22):
C, 42.65; H, 6.80. Found: C, 42.50; H, 6.75. Mp: 131 °C.
Complexation Studies. Reaction of 3 with 1 equiv of Ph4PI. A
131.0 mg portion (0.15 mmol, 1 equiv) of 3 and 49.0 mg (0.15 mmol,
1 equiv) of Ph4PI were dissolved in acetonitrile-d3/chloroform-d 1/1.
1H NMR (300.13 MHz, CD3CN/CDCl3, 293 K): δ 7.93−7.56 (m,
2
3J(1H−1H) = 7 Hz, J(1H−1H) = 9 Hz), 3.74−3.60 (m, 24 H, H4−
3
2
H9), 3.57 (dd, 4H, H3B/H10B, J(1H−1H) = 6 Hz, J(1H−1H) = 9
Hz), 2.63−2.55 (m, 2H, H2, 3J(1H−117/119Sn) = 159 Hz), 1.96 (d, 4H,
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20H, Ph4P+), 3.79 (dd, 4H, H3A/H12A, J(1H−1H) = 9.2 Hz,
J(1H−1H) = 7.0 Hz), 3.72−3.50 (m, 32H, H4−H11), 3.39 (dd, 4H,
H3B/H12B, J(1H−1H) = 9.0 Hz, J(1H−1H) = 7.5 Hz), 2.55−2.45 (m,
Reaction of 4 with 2 equiv of Ph4PBr in CDCl3. A 72.6 mg (92.3
μmol) portion of 4 and 44.4 mg (184.5 μmol) of Ph4PBr were
1
dissolved in 600 μL of CDCl3. H NMR (400.13 MHz, CDCl3): δ
7.89−7.77 (m, 8H, Ph4P+), 7.71 (td, 16H, Ph4P+, J = 7.78, 3.51 Hz),
7.53 (dd, 16H, Ph4P+, J = 13.05, 7.53 Hz), 3.73 (dd, 4H H3A/H12A,
2
2H, H2), 1.89 (d, 4H, H1, 3J(1H−1H) = 8.1 Hz, J(1H−117/119Sn)=85
Hz). 13C{1H} NMR (75.48 MHz, CD3CN/CDCl3, 293 K): δ 135.6
(d, J(13C−31P) = 3 Hz), 132.6 (d, J(13C−31P) = 325 Hz), 132.6 (d,
J(13C−31P) = 302 Hz), 118.3, 73.0 (3J(13C−117/119Sn) = 106 Hz), 70.5,
70.2, 70.1, 70.1, 37.4, 33.7. 119Sn{1H} NMR (111.92 MHz, CD3CN/
CDCl3, 293 K): δ −222.
3
2J(1H−1H) = 9 Hz, J(1H−1H) = 7 Hz), 3.68−3.43 (m, 32H, H4−
2
3
H11), 3.35 (dd, 4H, H3B/H12B, J(1H−1H) = 9 Hz, J(1H−1H) = 8
Hz), 2.50−2.39 (m, 2H, H2), 1.52 (d, 4H, H1, J(1H−1H) =8.03 Hz,
3
2J(1H−117/119Sn) = 94 Hz). 13C NMR (100.63 MHz, CDCl3): δ
135.53 (d, Ph4P+, J = 2.92 Hz), 134.00 (d, Ph4P+, J = 11 Hz), 130.54
(d, Ph4P+, J = 14 Hz), 117.00 (d, Ph4P+, J = 89 Hz), 73.41 (C3/C12,
3J(13C−117/119Sn) = 195 Hz), 70.34, 70.04, 69.79, 69.66, 36.14 (C2),
31.23 (C1).
Reaction of 3 with 2 equiv of Ph4PI: A 115.0 mg (0.13 mmol, 1
equiv) portion of 3 and 85.0 mg (0.27 mmol, 2 equiv) of Ph4PI were
dissolved in acetonitrile-d3/chloroform-d 1/1. 1H NMR (300.13 MHz,
CD3CN/CDCl3, 293 K): δ 7.93−7.58 (m, 40H, Ph4P+), 3.79 (dd, 4H,
H3A/H12A, J(1H−1H) = 9.0 Hz, J(1H−1H) = 76.8 Hz), 3.73−3.53
(m, 32H, H4−H11), 3.39 (dd, 4H, H3B/H12B, J(1H−1H) = 9.2 Hz,
J(1H−1H) = 7.7 Hz), 2.57−2.43 (m, 2H, H2), 1.88 (d, 4H, H1,
3J(1H−1H) = 8.4 Hz, 2J(1H−117/119Sn) = 85 Hz). 13C{1H} NMR
(75.48 MHz, CD3CN/CDCl3, 293 K): δ 135.6 (d, J(13C−31P) = 3
Hz), 132.6 (d, J(13C−31P) = 325 Hz), 132.6 (d, J(13C−31P) = 302 Hz),
Reaction of 4 with 2 equiv of NaClO4 in CDCl3. A 37.5 mg (48.5
μmol) portion of 4 and 11.9 mg (96.9 μmol) of NaClO4 were
1
dissolved in 600 μL of CDCl3. H NMR (400.13 MHz, CDCl3): δ
3.82−3.53 (m, 40H, H3−H12), 2.59−2.50 (m, 2H, H1,
3J(1H−117/119Sn) = 116 Hz), 1.79 (br s, 4H, H1, ν1/2= 23 Hz,
2J(1H−117/119Sn) = 80 Hz). 13C NMR (100.63 MHz, CDCl3): δ 74.77
(br s, ν1/2 = 30 Hz), 70.26, 69.99−69.76, 36.49 (C2), no C1 signal was
observed.
3
118.3, 73.0 (C3/C10, J(13C−117/119Sn) = 106 Hz), 70.5, 70.2, 70.1,
70.1, 37.4, 33.7. 119Sn{1H} NMR (111.92 MHz, CD3CN/CDCl3, 293
K): δ −222.
Reaction of 4 with 1 equiv of NaBr in CDCl3. A 10.2 mg (99.3
μmol) portion of NaBr was added to a solution of 78.2 mg (99.3
μmol) of 4 in 600 μL of CDCl3. 1H NMR (400 MHz, CDCl3): δ 3.78
Reaction of 3 with 2 equiv of Et4NF·2H2O. To a solution of 87 mg
(100 μmol) 3 in 600 μL of chloroform-d was added 37 mg (200 μmol)
1
2
3
(dd, 4H H3A/H12A, J(1H−1H) = 9 Hz, J(1H−1H) = 7 Hz), 3.73−
3.53 (m, 32H, H4−H11), 3.50 (m, dd, 4H, H3B/H12B, 2J(1H−1H) =
9 Hz, 3J(1H−1H) = 7 Hz), 2.63−2.49 (m, 2H, H2), 1.70 (d,
of Et4NF·2H2O. H NMR (300.13 MHz, CDCl3): δ 3.79 (dd, 4H,
2
3
H3A/H12A, J(1H−1H) = 9 Hz, J(1H−1H) = 7 Hz), 3.76−3.59 (m,
32H, H4−H11), 3.46 (dd, 4H, H3B/H12B, 2J(1H−1H) = 9 Hz,
3J(1H−1H) = 7 Hz), 3.44 (q, 16H, CH2N, 3J(1H−1H) = 7 Hz), 2.48−
2.38 (m, 2H, H2), 1.39 (tt, 24H, CH3CH2N, 3J(1H−1H) = 7 Hz, ?J = 2
Hz), 1.14 (d, 4H, H1, 3J(1H−1H) =8 Hz, 2J(1H−117/119Sn) = 100/104
Hz). 19F NMR (282.40 MHz, CDCl3): δ −166.8 (1J(19F−117/119Sn) =
2746/2889 Hz). 119Sn{1H} NMR (111.92 MHz, CDCl3): δ −236
(1J(119Sn−19F) = 2886 Hz).
3J(1H−1H)=8 Hz, 8 H, J(1H−117/119Sn) = 87 Hz).
2
Reaction of 4 with 1 equiv of NaBr in CD3CN. A 73.5 mg (95.1
μmol) portion of 4 and 9.8 mg (95.1 μmol) of NaBr were dissolved in
1
600 μL of CD3CN. H NMR (300 MHz, CD3CN): δ 3.82−3.20 (m,
3
40H, C3−C12), 2.83−2.59 (m, 2H, H2, J(1H−117/119Sn) = 105 Hz),
3
2
1.85 (d, 4H, H1, J(1H−1H) = 7 Hz, J(1H−117/119Sn) = 87/93 Hz).
119Sn{1H} NMR (111.92 MHz, CD3CN): δ −178.
Reaction of 4 with 1 equiv of NaBr in CD3OD. A 61.0 mg (78.9
μmol) portion of 4 and 8.1 mg (78.9 μmol) of NaBr were dissolved in
Reaction of 3 with 1 equiv of NaI in CD3CN. A 50.2 mg (58 μmol)
portion of 3 and 8.7 mg (58 μmol) of sodium iodide were dissolved in
1
600 μL of CD3CN. H NMR (400.13 MHz, CD3CN): δ 3.72−3.57
3
(m, 40H, H3−H12), 2.58−2.49 (m, 2H, H2, J(1H−117/119Sn) = 112
1
600 μL of CD3OD. H NMR (300.13 MHz, CD3OD): δ 3.85−3.54
3
2
Hz), 2.10 (d, 4H, H1, J(1H−1H) = 8 Hz, J(1H−117/119Sn) = 76/80
Hz). 13C{1H} NMR (100.63 MHz, CD3CN): δ 75.47 (C3/C12,
3J(1H−117/119Sn) = 87 Hz), 71.25, 70.67, 70.56, 70.48, 38.59 (C2,
2J(1H−117/119Sn) = 39 Hz), 36.25 (C1, br s, w1/2 = 4 Hz).
(m, 40H, H3−H12), 2.75−2.52 (m, 2H, H2, J(1H−117/119Sn) = 123
3
Hz), 1.84 (d, 4H, H1, 3J(1H−1H) = 4 Hz, 2J(1H−117/119Sn) = 123 Hz).
119Sn{1H}-NMR (111.92 MHz, CD3OD): δ −115.
Reaction of 4 with 2 equiv of of LaBr3·H2O in CD3CN. A 55 mg
(140 μmol) portion of LaBr3·H2O was added to a solution of 54.2 mg
(70.1 μmol) of 4 in 600 μL of CD3CN. 1H NMR (300 MHz,
CD3CN): δ 3.80 (dd, 4H H3A/H12A, 2J(1H−1H) = 9 Hz, 3J(1H−1H)
= 7 Hz), 3.76−3.48 (m, 32H, H4−H11), 3.40 (dd, 4H H3B/H12B,
2J(1H−1H) = 9 Hz, 3J(1H−1H) = 7 Hz), 2.55−2.43 (m, 2H, H2), 1.62
(d, 4H, H1, 3J(1H−1H) = 8 Hz, 2J(1H−117/119Sn) = 91/95 Hz).
119Sn{1H} NMR (111.92 MHz, CD3CN): δ −143.
Reaction of 3 with 2 equiv of NaI in CD3CN. A 79 mg (0.09 mmol,
1 equiv) portion of 3 and 27 mg (0.18 mmol, 2 equiv) of sodium
iodide were dissolved in acetonitrile-d3. 1H NMR (300.13 MHz,
2
3
CD3CN, 293 K): δ 3.73 (dd, J(1H−1H) = 9.5 Hz, J(1H−1H) = 1.8
Hz, 4H, CH2OCH2), 3.69−3.51 (m, 36H, CH2OCH2), 2.70−2.62 (m,
2H, SnCH2CHR), 2.38 (d, J(1H−1H) = 7.3 Hz, J(1H−117/119Sn) =
76 Hz), 4H, SnCH2CHR). 13C{1H} NMR (75.48 MHz, CD3CN, 293
K): δ 77.0 (3J(13C−117/119Sn) = 80 Hz), 70.3, 69.1, 69.0, 68.9, 39.9,
38.4 (1J(13C−117/119Sn) = 36 Hz). 119Sn{1H} NMR (111.92 MHz,
CD3CN, 293 K): δ −207.
3
2
Reaction of 4 with 1 equiv of MgBr2 in CD3CN. A 14.1 mg (76.7
μmol) portion of MgBr2 was added to a solution of 60.4 mg (76.7
1
μmol) of 4 in 600 μL of CD3CN. H NMR (400 MHz, CD3CN): δ
2
3
3.79 (dd, 4H H3A/H12A, J(1H−1H) = 9 Hz, J(1H−1H) = 7 Hz),
3.74−3.50 (m, 32H, H4−H11), 3.39 (dd, 4H H3B/H12B, 2J(1H−1H)
= 9 Hz, 3J(1H−1H) = 7 Hz), 2.55−2.43 (m, 2H, H2), 1.59 (d, 4H, H1,
Reaction of 3 with an Excess of NaI in D2O. A 30 mg (35 μmol)
portion of 3 and 50 mg (350 μmol, 10 equiv) of sodium iodide were
1
dissolved in 550 μL of D2O. H NMR (300.13 MHz, D2O): δ 4.09−
3J(1H−1H) = 8 Hz, J(1H−117/119Sn) = 92/95 Hz). 13C NMR (101
2
3.87 (m, 40H, H3−H12), 2.79 (m, 2H, H2), 2.06 (d, 4H, H1,
3J(1H−1H) = 8 Hz, J(1H−117/119Sn) = 60 Hz).
2
MHz, CD3CN): δ 74.13 (C3/C12, J(13C−117/119Sn) = 105/109 Hz),
3
71.15, 70.75, 70.72, 70.62, 37.17 (C2, J(13C−117/119Sn) = 34 Hz),
2
Reaction of 4 with 1 equiv of Ph4PBr in CDCl3. A 77.88 mg (98.9
μmol) portion of 4 and 41.48 mg (98.9 μmol) of Ph4PBr were
32.34 (C1).
1
dissolved in 600 μL of CDCl3. H NMR (400.13 MHz, CDCl3): δ
Reaction of 6 with 1 equiv of Et4NF·2H2O in CD3CN. A 76.7 mg
(0.12 mmol, 1 equiv) portion of 6 and 21.8 mg (0.12 mmol, 1 equiv)
of Et4NF·2H2O were dissolved in 600 μL of CD3CN. 1H NMR
(300.13 MHz, CD3CN, 293 K): δ 3.66−3.44 (m, 36H, H3A/H12A +
H4−H11), 3.37−3.32 (m, 4H, H3B/H12B), 3.18 (q, 8H, Et4N+,
3J(1H−1H) = 7.2 Hz), 2.26 (m, 2H, H2), 1.20 (tt, 12H, Et4NF+
J(1H−1H) = 7.2 Hz, J(1H−1H) = 1.9 Hz), 0.84 (d, 4H, H1,
3J(1H−1H) = 7.3 Hz, 2J(1H−117/119Sn) = 105.0/109.8 Hz). 19F−NMR
(282.38 MHz, CD3CN, 293 K): δ −126.0, −129.4, −150.8, −150.8,
−153.9. 119Sn{1H} NMR (111.92 MHz, CD3CN, 293 K): no
resonance observed.
7.80−7.89 (m, 4H, Ph4P+), 7.72 (td, 8H, Ph4P+, J = 7.78, 3.51 Hz),
7.54 (dd, 8H, Ph4P+, J = 12.92, 7.40 Hz), 3.73 (dd, 4H, H3A/H12A,
3
2J(1H−1H) = 9 Hz, J(1H−1H) = 7 Hz), 3.45−3.68 (m, 32H), 3.36
2
3
(dd, 4H, H3B/H12B, J(1H−1H) = 9 Hz, J(1H−1H) = 8 Hz), 2.46
(m, 2H, H2), 1.53 (d, 4H, H1, 3J(1H−1H) = 8 Hz, 2J(1H−117/119Sn) =
93 Hz). 13C{1H} NMR (100.63 MHz, CDCl3): δ 135.56 (d,
J(13C−31P) = 3 Hz), 134.04 (d, J(13C−31P) = 11 Hz), 130.56 (d,
J(13C−31P) = 13 Hz), 117.02 (d, J(13C−31P) = 89 Hz), 73.44 (C3/
3
C12, J(13C−117/119Sn) = 195 Hz), 70.35, 69.94, 69.90, 69.68, 36.17
3
(C2, J(13C−117/119Sn) = 35 Hz), 31.25 (C1, br s).
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2
Reaction of 6 with 2 equiv of Et4NF·2H2O in CD3CN. A 84.1 mg
(0.13 mmol) portion of 6 and 47.8 mg (0.26 mmol, 2 equiv) of
Et4NF·2H2O were dissolved in 600 μL of CD3CN. H NMR (300.13
3.54 (m, 32 H, H4−H9), 3.51 (dd, 4H, H3A/H10A, J(1H−1H) = 9
Hz, J(1H−1H) = 6 Hz), 2.56 (m, 2H, H2, J(1H−117/119Sn) = 148
3
3
Hz), 1.93 (d, 4H, H1, J(1H−1H) = 7 Hz, J(1H−117/119Sn) = 83/86
Hz). 13C NMR (100.63 MHz, CD3CN): δ 72.02 (C3/C10), 71.23,
70.89, 70.40, 38.15 (C2), 33.78 (C1).
1
3
2
MHz, CD3CN, 293 K): δ 3.63−3.42 (m, 36H, H3A/H12A + H4−
H11), 3.36−3.30 (m, 4H, H3B/H12B), 3.20 (q, 16H, Et4N+,
3J(1H−1H) = 7.3 Hz), 2.23 (m, 2H, H2), 1.20 (tt, 24 H, Et4N+,
J(1H−1H) = 7.3 Hz, J(1H−1H) = 1.8 Hz), 0.79 (d, 4H, H1,
3J(1H−1H) = 7.3 Hz, 2J(1H−117/119Sn) = 106.1 Hz). 19F NMR (282.38
Reaction of 10 with 2 equiv of LiI in CD3CN. A 21.1 mg (158
μmol) portion of LiI was added to a solution of 61.5 mg (79 μmol) of
1
10 in 600 μL of CD3CN. H NMR (400.13 MHz, CD3CN): δ 3.89
(dd, 4H, H3A/H10A, J(1H−1H) = 9 Hz, J(1H−1H) = 3 Hz), 3.81−
2
3
2
MHz, CD3CN): δ −126.70, −129.06 (d, J(19F−19F) = 16.06 Hz,
2
1J(19F−117/119Sn) = 2599/2720 Hz), −136.05 (quintet, J(19F−19F) =
3.58 (m, 28H, H4−H9 + H3B/H10B), 2.80−2.68 (m, 2H, H2,
3J(1H−117/119Sn) = 142 Hz), 2.25 (d, 4H, H1, J(1H−1H) = 7 Hz,
3
1
16.06 Hz, J(19F−117/119Sn) = 1170 Hz), −150.73, −150.79, −153.7.
2J(1H−117/119Sn) = 70 Hz). 13C NMR (100.63 MHz, CD3CN): δ
119Sn{1H} NMR (111.92 MHz, CD3CN): δ −330 (w1/2 = 518 Hz).
Reaction of 6 with 1 equiv of Et4NF·2H2O in CD2Cl2 at 213 K. A
61.2 mg (0.094 mmol) portion of 6 and 17.4 mg (0.094 mmol) of
Et4NF·2H2O were dissolved in 600 μL of CD2Cl2, and the resulting
solution was investigated by NMR spectroscopy at 213 K. 19F NMR
(282.38 MHz, CD2Cl2, 213 K): δ −117.8 (s, 1J(19F−117/119Sn) =
2522/2645 Hz), −160.5 (s, 1J(19F−117/119Sn) = Hz),−164.7 (br s,
1J(19F−117/119Sn) = Hz). 119Sn{1H} NMR (111.92 MHz, CD2Cl2, 213
76.07 (C3/C10, J(13C−117/119Sn) = 80/84 Hz), 69.21, 68.32, 68.07,
3
39.07 (br s, C1, ν1/2 = 8 Hz), 38.17 (C2, 2J(13C−117/119Sn) = 38 Hz).
119Sn NMR (111.92 MHz, CD3CN): δ −216 (ν1/2 = 243 Hz).
Reaction of 10 with an Excess of NaI in CD3CN. A 50.0 mg (334
μmol) portion of NaI was added to a solution of 60.0 mg (77 μmol) of
1
10 in 600 μL of CD3CN. H NMR (400.13 MHz, CD3CN): δ 3.87
(dd, 4H, H3A/H10A, J(1H−1H) = 9 Hz, J(1H−1H) = 7 Hz), 3.73−
2
3
2
3.54 (m, 32 H, H4−H9), 3.51 (dd, 4H, H3A/H10A, J(1H−1H) = 9
1
1
K): δ −333 (q, J(119Sn−19F) = 2656 Hz), −242 (t, J(119Sn−19F) =
Hz, J(1H−1H) = 6 Hz), 2.56 (m, 2H, H2, J(1H−117/119Sn) = 148
3
3
2892 Hz).
Hz), 1.93 (d, 4H, H1, J(1H−1H) = 7 Hz, J(1H−117/119Sn) = 83/86
Hz). 13C{1H} NMR (100.63 MHz, CD3CN): δ 72.02 (C3/C10),
71.23, 70.89, 70.40, 38.15 (C2), 33.78 (C1).
3
2
Reaction of 6 with 2 equiv of Et4NF·2H2O in CD2Cl2 at 213 K. A
65.4 mg (0.100 mmol) portion of 6 and 37.2 mg (0.201 mmol) of
Et4NF·2H2O were dissolved in 600 μL of CD2Cl2, and the resulting
solution was investigated by NMR spectroscopy at 213 K. 19F NMR
Reaction of 11 with 1 equiv of LiBr in CD3CN. A 6.9 mg (80 μmol)
portion of LiBr was added to a solution of 54.7 mg (80 μmol) of 11 in
600 μL of CD3CN. 1H NMR (300.13 MHz, CD3CN, 293 K): δ 3.80−
2
(282.38 MHz, CD2Cl2, 213 K): δ −118.1 (d, J(19F−19F) = 18.4 Hz,
3J(19F−117/119Sn) = 2547/2647 Hz), −159.7 (t, 2J(19F−19F) = 22.9 Hz,
3J(19F−117/119Sn) = 2552/2666 Hz) (+ signals without coupling to
117/119Sn at δ −128.04, −129.84, −129,89, −151.00, −151.12,
−151.54). 119Sn{1H} NMR (111.92 MHz, CD2Cl2, 213 K): δ −333
3.54 (m, 32H, H3−H10), 2.85−2.67 (m, 2H, H2, J(1H−117/119Sn) =
3
149 Hz), 1.81 (d, 4H, H1, 3J(1H−1H) = 7 Hz, 2J(1H−117/119Sn) = 89/
1
93 Hz). H NMR (300.13 MHz, CD3CN, 253 K): δ 3.81−3.48 (m,
32H, H3−H10), 2.82−2.62 (m, 2H, H2, 2J(1H−117/119Sn) = 145 Hz),
1.76 (d, 4H, 3J(1H−1H) = 7 Hz, 2J(1H−117/119Sn) = 94 Hz). 119Sn{1H}
NMR (111.92 MHz, CD3CN, 293 K): δ −172 (ν1/2 = 227 Hz).
Reaction of 11 with an Excess of LiBr in CD3OD. A 19.8 mg
portion of LiBr werewas added to a solution of 30.2 mg of 11 in 600
1
(q, J(119Sn−19F) = 2662 Hz).
Reaction of 6 with an Excess of LiF in CDCl3. An excess of LiF was
added to a solution of 6 in 600 μL of CDCl3. 1H NMR (200.13 MHz,
CDCl3, 293 K): δ 3.82−3.55 (m, 36H, H3A/H12A + H4−H11),
3.49−3.41 (m, 4H, H3B/H12B), 2.42 (m, 2H, H2), 1.14 (d, 4H, H1,
1
μL of CD3OD. H NMR (400.13 MHz, CD3OD): δ 3.91 (dd, 2H,
2
3J(1H−1H) = 8.06 Hz, J(1H−117/119Sn) = 99.7/103.6 Hz). 19F NMR
2J(1H−1H) = 9 Hz, 3J(1H−1H) = 7 Hz), 3.82 (dd, 4H, 2J(1H−1H) = 9
Hz, 3J(1H−1H) = 7 Hz), 3.77−3.56 (m, 26H), 2.57−2.69 (m, 2H, H2,
3J(1H−1H) = 172 Hz), 1.68 (d, 4H, H1, 3J(1H−1H) = 7 Hz,
2J(1H−117/119Sn) = 89/94 Hz). 13C{1H} NMR (100.63 MHz,
CD3OD): δ 72.39 (C3/C10), 71.44, 71.21, 70.65, 37.72 (C2), 31.71
(C1).
(188.28 MHz, CDCl3, 293 K): δ −168.86 (s, 1J(19F−117/119Sn) =
2751.1/2893.2 Hz).
Reaction of 6 with 1 equiv of NaF in CD3CN. A 2.5 mg (0.06
mmol) portion of NaF was added to a solution of 39.1 mg (0.06
1
mmol) of 6 in 600 μL of CD3CN. H NMR (200.13 MHz, CD3CN,
293 K): δ 3.77−3.51 (m, 36H, H3A/H12A + H4−H11), 3.43−3.34
(m, 4H, H3B/H12B), 2.33 (m, 2H, H2), 1.05 (d, 4H, H1, 3J(1H−1H)
Reaction of 11 with 1 equiv of CsClO4 in CD3CN. A 17.4 mg (75
μmol) portion of CsClO4 was added to a solution of 51.4 mg (75
μmol)of 11 in 600 μL of CD3CN. 1H NMR (300.13 MHz, CD3CN):
δ 3.80 (dd, 4H, H3A/H10A, 2J(1H−1H) = 9 Hz, 3J(1H−1H) = 7 Hz),
3.73−3.47 (m, 28H, H4−H9+H3B/H10B), 2.59 (m, 2H, H2,
2
= 8.06 Hz, J(1H−117/119Sn) = 99.0/103.3 Hz).
Reaction of 6 with 2 equiv of NaF in CD3CN. A 4.9 mg (0.12
mmol) portion of NaF was added to a solution of 38.3 mg (0.06
1
mmol) of 6 in 600 μL of CD3CN. H NMR (200.13 MHz, CD3CN,
3J(1H−117/119Sn) = 165 Hz), 1.65 (d, 4H, H1, J(1H−1H) = 7 Hz,
3
293 K): δ 3.77−3.51 (m, 36H, H3A/H12A + H4−H11), 3.43−3.34
2J(1H−117/119Sn) = 90/94 Hz). 119Sn{1H} NMR (111.92 MHz,
CD3CN): δ −147 (ν1/2 = 25 Hz).
(m, 4H, H3B/H12B), 2.33 (m, 2H, H2), 1.05 (d, 4H, H1, 3J(1H−1H)
2
= 7.82 Hz, J(1H−117/119Sn) = 98.7/103.1 Hz).
Reaction of 12 with an Excess of LiF in CD3CN. A 10 mg (385
μmol) portion of LiF was added to a solution of 30 mg (53 μmol) of
Reaction of 6 with 2 equiv of CsF in CD3CN. An 18.1 mg (0.12
mmol) portion of CsF was added to a solution of 77.8 mg (0.12
1
1
12 in 600 μL of CD3CN. H NMR (200.13 MHz, CD3CN): δ 3.84−
mmol) of 6 in 600 μL of CD3CN. H NMR (300.13 MHz, CD3CN,
3.34 (m, 32H, H3−H10), 2.62−2.35 (m, 2H, H2, J(1H−117/119Sn) =
3
293 K): δ 3.70−3.54 (m, 36H, H3A/H12A + H4−H11), 3.43−3.37
(m, 4H, H3B/H12B), 2.33 (m, 2H, H2), 1.02 (d, 4H, H1, 3J(1H−1H)
= 7.7 Hz, 2J(1H−117/119Sn) = 101.0/104.3 Hz). 19F NMR (282.38
MHz, CD3CN): δ −150.8 (no coupling to 119/117Sn observed).
119Sn{1H} NMR (111.92 MHz, CD3CN): no resonance observed.
Reaction of 6 with 1 equiv of CsF in CD3OD. A 19.1 mg (0.126
mmol) portion of CsF was added to a solution of 81.8 g (0.126 mmol)
of 6 in 600 μL of CD3OD, and the solution was investigated by NMR
spectroscopy at 213 K. 19F NMR (282.38 MHz, CD3OD, 213 K): δ
−126 (?), −152 (CsF), −160 (br s). 119Sn{1H} NMR (111.92 MHz,
182/194 Hz), 1.19 (d, 4H, H1, 3J(1H−1H) = 5 Hz, 2J(1H−117/119Sn) =
98 Hz). 13C NMR (75.47 MHz, CD3CN): δ 72.03 (C3/C10,
3J(13C−117/119Sn) = 59 Hz), 70.87, 70.60, 70.08, 36.22 (C2,
2J(13C−117/119Sn) = 33 Hz), 20.49 (br s, C1, ν1/2 = 33 Hz). 19F
NMR (188.29 MHz, CD3CN): δ −152.2 (3%), −165 (97%,
1J(19F−117/119Sn) = 2760 Hz). 119Sn NMR (111.92 MHz, CD3CN):
1
δ −235 (t, J(119Sn−19F) = 2822 Hz).
Reaction of 12 with an Excess of CsF in CDCl3. A 40 mg (263
μmol) portion of CsF was added to a solution of 30 mg (53 μmol) of
12 in 600 μL of CDCl3. 1H NMR (200.13 MHz, CDCl3): δ 3.72−3.49
(m, 32H, H3−H10), 2.58−2.33 (m, 2H, H2), 1.11 (d, 3J(1H−1H) = 6
1
CD3OD, 213 K): δ −256 (t, J(19F−119Sn) = 2918 Hz), −337 (q,
1J(19F−119Sn) = 2684 Hz).
2
Reaction of 10 with 2 equiv of CsI in CD3CN. A 40.0 mg (154
μmol) portion of CsI was added to a solution of 60.0 mg (77 μmol) of
Hz, J(1H−117/119Sn) = 102 Hz, 4H, H1). 19F NMR (188.29 MHz,
CDCl3): no signal observed.
1
10 in 600 μL of CD3CN. H NMR (400.13 MHz, CD3CN): δ 3.87
Reaction of 12 with 1 equiv of AgF in CD3CN. A 6.5 mg (52 μmol)
portion of AgF was added to a solution of 29.1 mg (52 μmol) of 12 in
(dd, 4H, H3A/H10A, 2J(1H−1H) = 9 Hz, 3J(1H−1H) = 7 Hz), 3.73−
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600 μL of CD3CN. H NMR (200.13 MHz, CD3CN): δ 3.74−3.36
(16) (a) Tagne Kuate, A. C.; Iovkova, L.; Hiller, W.; Schurmann, M.;
̈
(m, 32H), 2.41−2.17 (m, 2H, H2, J(1H−117/119Sn) = 145 Hz), 1.02
Jurkschat, K. Organometallics 2010, 29, 5456−5471. (b) Kemmer, M.;
Ghys, L.; Gielen, M.; Biesemans, M.; Tiekink, E. R. T.; Willem, R. J.
Organomet. Chem. 1999, 582, 195−203.
3
(d, 4H, H1, 3J(1H−1H) = 7 Hz, 2J(1H−117/119Sn) = 105/108 Hz). 13
C
NMR (75.47 MHz, CD3CN): δ 72.97 (s, 1 C), 72.19 (s, 2 C), 70.56
(s, 2 C), 70.19−70.41 (m, 7 C), 69.85 (d, J = 2 Hz, 5 C), 36.20 (s, 1
C), 35.98 (s, 1 C), 24.05 (s, 1 C). 19F NMR (188.29 MHz, CD3CN):
δ −129 (br. s, ν1/2 = 152 Hz, 80%), −130 (s, 20%).
(17) Bondi, A. J. Phys. Chem. 1964, 68 (3), 441−451.
(18) Schlecht, S.; Dinnebier, R.; Friese, K. Z. Anorg. Allg. Chem. 2002,
628 (4), 725−727.
Crystallography. Intensity data for crystals of 4−6, 10, and 12
were collected on a XcaliburS CCD diffractometer (Oxford
Diffraction) and for crystal 11 on a SMART APEX2 CCD
diffractometer (Bruker) using Mo Kα radiation at 110 K. All structures
were solved with direct methods using SHELXS-97.26 Refinements
were carried out against F2 by using SHELXL-97.26 The C−H
hydrogen atoms were positioned with idealized geometries and refined
using a riding model. All non-hydrogen atoms were refined using
anisotropic displacement parameters. In compound 11 Sn1 and Br1
are disordered and split into two positions. Their occupancies were
allowed to refine freely until a constant number was obtained (second
FVAR 0.87544). For decimal rounding of numerical parameters and su
values the rules of IUCr have been employed.27
(19) (a) Ganis, P.; Valle, G.; Furlani, D.; Tagliavini, G. J. Organomet.
Chem. 1986, 302, 165−170. (b) Ye, F.; Reuter, H. Acta Crystallogr.
2012, C68, m104−m108.
(20) Konig, U.-C.; Berkei, M.; Neikes, N.; Preut, H.; Mitchell, T. N.
̈
Acta Crystallogr. 2000, C56, 324−326.
(21) Blunden, St. J.; Frangout, A.; Gillies, D. G. Org. Magn. Reson.
1982, 20, 170−174.
(22) Kong, X.; Grindley, T. B.; Bakashi, P. K.; Cameron, T. S.
Organometallics. 1993, 12, 4881−4886.
(23) Van Den Berghe, E. V.; Van Der Kelen, G. P. J. Organomet.
Chem. 1971, 26, 207−213.
(24) Kennedy, J. D., McFarlane, W. NMR and the Periodic Table;
Academic Press: London, 1978; p 342.
CCDC-902174 (4), CCDC-902175 (5), CCDC-902176 (6),
CCDC-902177 (10), CCDC-902178 (11) and CCDC-902179 (12)
contain supplementary crystallographic data for this paper. This data
can be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
(25) (a) Otera, J.; Yano, Y.; Kusakabe, K. J. Chem. Soc. Jpn. 1983, 56,
1057−1059. (b) Steed, J. W. Coord. Chem. Rev. 2001, 215, 171−221.
(26) Sheldrick, G. M. Acta Crystallogr., Sect. A 2008, 64, 112−122.
(27) Clegg, W. Acta Crystallogr., Sect. E 2003, 59, e2−e5.
ASSOCIATED CONTENT
■
S
* Supporting Information
CIF files for compounds 4−6 and 10−12, molecular structures
1
for 5, 6, 10, and 12 (Figures S1−S4), H, 19F, and 119Sn NMR
spectra of 6 (Figures S5−S7), and crystallographic data (Tables
S1 and S2). This material is available free of charge via the
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to an anonymous reviewer for valuable hints.
REFERENCES
■
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