Synthesis of Mono-, Bis- and Tris(pentafluoroethyl)tin Derivatives, (C2F5)4?nSnXn (X=Ph, Me, Cl, Br, Cp; n=1–3)

Article abstract of DOI:10.1002/chem.201701270

For (pentafluoroethyl)phenylstannanes, (C₂F₅)_4?n SnPh_n (n=1–3), and dimethylbis(pentafluoroethyl)stannane, (C₂F₅)₂SnMe₂, a high yield synthesis was developed by the use of LiC₂F₅ as a C₂F₅ transfer reagent. The treatment of these products with gaseous hydrogen chloride or hydrogen bromide afforded (C₂F₅)_4?nSnX_n (X=Cl, Br; n=1–3) in good yields. The (pentafluoroethyl)stannanes were fully characterized by ¹H, ¹³C, ¹⁹F and ¹¹⁹Sn NMR, IR spectroscopy and mass spectrometry. The treatment of the (pentafluoroethyl)tin halides (C₂F₅)_4?nSnX_n with 1,10-phenanthroline (phen) led to the formation of the corresponding octahedrally coordinated complexes [(C₂F₅)_4?nSnX_n(phen)], the structures of which were elucidated by X-ray diffraction analyses. The bromostannane (C₂F₅)₃SnBr reacted with sodium cyclopentadienide to give the (η¹-cyclopentadienyl)tris(pentafluoroethyl)stannane, (C₂F₅)₃SnCp, for which single-crystal X-ray diffraction analysis could be performed. The coupling constants ¹J(¹¹⁹Sn,¹³C) and ²J(¹¹⁹Sn,¹⁹F) of all new stannanes are strongly correlated and sensitive to the substitution pattern at the tin atom. For both coupling constants a negative sign could be assigned.

Full text of DOI:10.1002/chem.201701270

A Journal of
Accepted Article
Title: Synthesis of Mono-, Bis- and Tris(pentafluoroethyl)tin Derivatives,
(C2F5)4−nSnXn (X = Ph, Me, Cl, Br, Cp; n = 1-3)
Authors: Johannes Klösener, Markus Wiesemann, Mark Niemann,
Beate Neumann, Hans-Georg Stammler, and Berthold Hoge
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Synthesis of Mono-, Bis- and Tris(pentafluoroethyl)tin
Derivatives, (C2F5)4−nSnXn (X = Ph, Me, Cl, Br, Cp; n = 1-3)
Johannes Klösener, Markus Wiesemann, Mark Niemann, Beate Neumann, Hans-Georg Stammler and
Berthold Hoge*
Dedicated to Prof. Dr. Helge Willner on the occasion of his 70th birthday
Abstract: For (pentafluoroethyl)phenylstannanes, (C2F5)4−nSnPhn
(n = 1-3), and dimethylbis(pentafluoroethyl)stannane, (C2F5)2SnMe2, a
high yield synthesis was developed by the use of LiC2F5 as a C2F5
transfer reagent. The treatment of these products with gaseous
hydrogen chloride or hydrogen bromide afforded (C2F5)4-nSnXn (X = Cl,
Scheme 1. Synthesis of bromo(trifluoromethyl)stannanes, (CF3)4-nSnBrn
(n = 1-3) and tetrakis(trifluoromethyl)stannane Sn(CF3)4.
Br; n = 1-3) in good yields. The (pentafluoroethyl)stannanes were fully
characterized by 1H, 13C, 19F and 119Sn NMR, IR spectroscopy and
mass spectrometry.
The treatment of the (pentafluoroethyl)tin halides (C2F5)4-nSnXn
Cullen et al. investigated the thermal decomposition of
with 1,10-phenanthroline (phen) led to the formation of the
trimethyl(perfluoroalkyl)stannanes, RfSnMe3 (Rf = CF3, C2F5,
corresponding
octahedrally
coordinated
complexes
CF(CF3)2). In contrast to trifluoromethyl and heptafluoroisopropyl
substituted stannanes, which decompose at 150 °C, more than
90 % of the trimethyl(pentafluoroethyl)stannane, (C2F5)SnMe3,
could be recovered after heating for 72 hours at 200 °C.[3] This
[(C2F5)4-nSnXn(phen)], the structures of which were elucidated by X-ray
diffraction analyses.
The bromostannane (C2F5)3SnBr was reacted with sodium
cyclopentadienide
to
give
the
(η1-cyclopentadienyl)-
illustrates
the
particularly
high
thermal
stability
of
tris(pentafluoroethyl)stannane, (C2F5)3SnCp. A single crystal was
grown by in situ crystallization and used for X-ray diffraction analysis.
The coupling constants 1J(119Sn,13C) and 2J(119Sn,19F) of all new
stannanes are strongly correlated and sensitive to the substitution
pattern at the tin atom. For both coupling constants a negative sign
could be assigned.
(pentafluoroethyl)stannanes. However, little work has been
published on (pentafluoroethyl)tin halides.
The first (pentafluoroethyl)stannanes (C2F5)SnR3 (R = Me, Et,
Ph) were synthesized in yields up to 22 % by reacting hexaalkyl-
or hexaphenyldistannane with C2F5I.[4] In 1968 Kawakami and
Kuivila succeeded in generating LiC2F5 from MeLi and C2F5I and
the subsequent transfer of the C2F5 unit onto allyl tin and lead
compounds.[5] The generation of LiC2F5 and its reaction with
organotin halides was improved by Falck et al. reaching yields up
to 88 %.[6] Reacting donor stabilized bis(pentafluoroethyl)-
cadmium, Cd(C2F5)2∙D, with trifluoroacetato- or nitratotrimethyl-
stannane furnished (C2F5)SnMe3 in moderate yields.[7] Although
Mehrabani et al. employed AgC2F5 or (C2F5)SiMe3 as transfer
reagents, only small amounts of (pentafluoroethyl)tin halides were
formed. No attempts of optimization or isolation of these products
were made.[8] LiC2F5 was also generated from C2F5H and n-BuLi in
diethyl ether at −78 °C (Scheme 2). At temperatures above −40 °C
decomposition of this compound to C2F4 und LiF was observed.[9]
Introduction
The replacement of electron donating alkyl by electron withdrawing
perfluoroalkyl groups has dramatic effects on the electronic nature
of an organoelement compound and usually is accompanied by a
significant stabilization of these types of compounds. As a
consequence, electron deficient tin compounds exhibit an
increased Lewis acidity compared to alkylstannanes.
(Trifluoromethyl)stannane derivatives, (CF3)4−nSnXn (X = F, Cl, Br,
I; n = 0-3), were synthesized and studied extensively by Eujen et
al.[1] The treatment of SnBr4 with the toxic reagents Cd(CF3)2 or
Hg(CF3)2 led to a series of different bromo(trifluoromethyl)-
stannanes, (CF3)4-nSnBrn (n = 0-3) as well as Sn(CF3)4 (Scheme 1).
However, these (trifluoromethyl)stannanes are highly sensitive
towards difluorocarbene elimination and dismutation reactions.[2]
Scheme 2. Synthesis and decomposition of pentafluoroethyllithium, LiC2F5.
Herein, we report on the selective synthesis of
(pentafluoroethyl)phenylstannanes, (C2F5)4−nSnPhn (n = 1-3), by
the reaction of LiC2F5 with the corresponding chlorophenyl-
stannanes, Cl4−nSnPhn. The cleavage of the Sn-Ph bond with
gaseous hydrogen halides HX (X = Cl, Br) leads to the
corresponding (pentafluoroethyl)tin halides, (C2F5)4-nSnXn (n = 1-3).
Dr. J. Klösener, M. Wiesemann, M. Niemann, B. Neumann,
Dr. H.-G. Stammler, Prof. Dr. B. Hoge
Universität Bielefeld
Fakultät für Chemie, Anorganische Chemie II
Universitätsstraße 25, 33615 Bielefeld (Germany)
E-mail: b.hoge@uni-bielefeld.de
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These species form adducts [(C2F5)4-nSnXn(phen)] (X = Br, n = 1-
3; X = Cl, n = 1-2) with the chelating ligand 1,10-phenanthroline
(phen).
By the reaction of (C2F5)3SnPh with gaseous hydrogen bromide at
130 °C, the desired bromostannane (C2F5)3SnBr was prepared in
an 88 % yield as a colorless liquid and a vapor pressure of 15 mbar
at 23 °C (Scheme 4).
Results and Discussion
The employment of LiC2F5 as
a transfer reagent of the
pentafluoroethyl group requires temperatures below −40 °C.
Pentafluoroethyllithium was prepared in situ at −78 °C by the
combination of n-BuLi with pentafluoroethane in a diethyl ether
solution. The addition of SnCl4 to this mixture results in the
precipitation of a colorless solid, which presumably is the diethyl
ether adduct of the Lewis acidic SnCl4. Under these conditions, no
selective reaction could be achieved, but this reaction is still under
investigation in our laboratory. As expected, the substitution of one
chlorine atom by a phenyl group leads to a decreased Lewis acidity.
In keeping with this, no insoluble diethyl ether adduct of Cl3SnPh
was formed and the reaction of Cl3SnPh with 3.5 equivalents of
LiC2F5 selectively afforded tris(pentafluoroethyl)phenylstannane,
(C2F5)3SnPh. The product was isolated by distillation and obtained
as a colorless liquid in an 83 % yield (Scheme 3).
Scheme 4. Synthesis of (pentafluoroethyl)tin halides, (C2F5)4-nSnXn (X = Cl, Br;
n = 1-3).
Analogously, the corresponding chlorostannane (C2F5)3SnCl
was obtained by the conversion of the phenylstannane
(C2F5)3SnPh with hydrogen chloride at 170 °C in an 82 % yield as
a colorless liquid and a slightly higher vapor pressure of 25 mbar
at 23 °C. The tin carbon bonds to the aryl groups in
bis(pentafluoroethyl)diphenylstannane, (C2F5)2SnPh2, are shielded
by only two C2F5 groups. Therefore the temperature of the reaction
with HBr was reduced to 100 °C and (C2F5)2SnBr2 was isolated in
an 84 % yield. A vapor pressure of 20 mbar of the colorless liquid
was measured at 23 °C. (C2F5)2SnCl2 and (C2F5)SnBr3 were also
accessible via the solvent free reaction of the corresponding
phenylstannanes with the HCl and HBr, respectively.
In order to obtain structural parameters of the novel
(pentafluoroethyl)tin halides the compounds were converted into
their 1,10-phenanthroline (phen) adducts. Adduct formation of
(trifluoromethyl)tin halides, (CF3)4-nSnXn (X = F, Cl, Br; n = 1-3),
with 1,10-phenanthroline was previously reported by Eujen and
Thurmann.[1,12] Similarly, octahedrally configurated adducts of the
Scheme 3. Synthesis of (pentafluoroethyl)phenylstannanes, (C2F5)4-nSnPhn
(n = 1-3).
(pentafluoroethyl)tin
halides
(C2F5)3SnBr,
(C2F5)3SnCl,
(C2F5)2SnBr2, (C2F5)2SnCl2 and (C2F5)SnBr3 were synthesized by
the reaction with 1,10-phenanthroline in dichloromethane or
acetonitrile solution (Scheme 5). Recrystallization of the products
from dichloromethane or acetonitrile provided single crystals
suitable for X-ray structure analyses. The formation of the
1,10-phenathroline adducts of the Lewis acidic stannanes thus
constitutes a useful method for the identification of Lewis acidic
stannanes.
Bis(pentafluoroethyl)diphenylstannane, (C2F5)2SnPh2, and
(pentafluoroethyl)triphenylstannane,
(C2F5)SnPh3,
were
synthesized analogously from LiC2F5 and Cl2SnPh2 and ClSnPh3,
respectively. The employed protocol is also applicable for the
synthesis of methyl substituted stannanes. Accordingly, dimethyl-
bis(pentafluoroethyl)stannane, (C2F5)2SnMe2, was prepared in an
86 % yield as a colorless liquid with a vapor pressure of 15 mbar
at 20 °C.
In order to obtain functionalized perfluoroalkylstannanes, the
phenyl group had to be replaced by halogen atoms. Generally, the
tin carbon bond of (perfluoroalkyl)organylstannane derivatives can
be cleaved under relatively mild conditions by the use of elemental
halogens X2 or hydrogen halides HX.[6] Jahn et al. reported the
quantitative conversion of (CF3)3SnPh with elemental bromine at
−15 °C.[2] Interestingly here, however, the addition of a large
excess of bromine to a solution of (C2F5)3SnPh in chloroform did
not lead to any observable reaction at room temperature even after
a prolonged reaction time. This difference in reactivity can possibly
be explained by the kinetic stabilization of the tin carbon bond
provided by the increased steric hindrance of the pentafluoroethyl
groups. A similar effect was described for P(CF3)3 and P(C2F5)3.
Tolman determined a cone angle of 137° for the P(CF3)3 ligand,[10]
while the P(C2F5)3 molecule exhibits a cone angle of 193° in the
solid state and of 191° in the gas phase.[11]
Scheme 5. Synthesis of 1,10-phenanthroline adducts of (pentafluoroethyl)tin
halides, [(C2F5)4-nSnXn(phen)] (X = Br, n = 1-3; X = Cl, n = 1-2).
The compounds [(C2F5)3SnBr(phen)], [(C2F5)3SnCl(phen)]
and [(C2F5)SnBr3(phen)] crystallize in the monoclinic space group
P21/n
and
the
compounds
[(C2F5)2SnBr2(phen)]
and
[(C2F5)2SnCl2(phen)] crystallize in the orthorhombic space group
Pbca. The molecular structures are shown in Figure 1. Selected
bond lengths are given in Table 1 and crystal data and refinement
characteristics are given in Table 3.
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Figure 1. Molecular structures of the 1,10-phenanthroline adducts of bromo(pentafluoroethyl)stannanes (top) [(C2F5)3SnBr(phen)] (left), [(C2F5)2SnBr2(phen)]
(middle) and [(C2F5)SnBr3(phen)] (right), and of the 1,10-phenanthroline adducts of chloro(pentafluoroethyl)stannanes (bottom) [(C2F5)3SnCl(phen)] (left),
[(C2F5)2SnCl2(phen)] (right); 50 % probability amplitude displacement ellipsoids are shown; selected bond lengths [pm] are given in Table 1.
In the series of [(C2F5)3SnBr(phen)], [(C2F5)2SnBr2(phen)],
[(C2F5)SnBr3(phen)] (Figure 1) and [SnBr4(phen)][13] an increasing
number of bromine atoms is accompanied by a not very significant
shortening of the Sn-N distance from 231 pm for
[(C2F5)3SnBr(phen)] to 226 pm for [SnBr4(phen)]. The same
tendency is observed for the corresponding chloro derivatives.
These observations lead to the conclusion that the substitution of
a bromine or a chlorine atom by the pentafluoroethyl group
reduces the Lewis acidity of the resulting stannane. As expected
the Sn-N bond of [Me2SnCl2(phen)][15] is elongated significantly by
approximately 11 pm in comparison to [(C2F5)2SnCl2(phen)] which
is due to an increased Lewis acidity in the perfluoroalkyl
derivatives compared to the non-fluorinated alkylstannanes.
The (pentafluoroethyl)tin halides (C2F5)4-nSnXn (X = Cl, Br)
are useful starting materials for the synthesis of a wide variety of
(pentafluoroethyl)stannane derivatives. The solvent free
conversion of (C2F5)3SnBr with sodium cyclopentadienide at
ambient temperature selectively afforded (η1-cyclopentadienyl)-
tris(pentafluoroethyl)stannane, (C2F5)3SnCp, which was isolated
in a 76 % yield (Scheme 6).
Scheme 6. Synthesis of (η1-cyclopentadienyl)tris(pentafluoroethyl)stannane,
(C2F5)3SnCp.
Table 1. Selected bond lengths of 1,10-phenanthroline adducts of (pentafluoroethyl)tin halides [(C2F5)4-nSnXn(phen)] (X = Br, n = 1-3; X = Cl, n = 1-2) and literature
known stannanes [pm].
[13]
[14]
[15]
(C2F5)3SnBr (10)
(C2F5)2SnBr2 (12)
(C2F5)SnBr3 (14)
SnBr4
(C2F5)3SnCl (11)
(C2F5)2SnCl2 (13)
SnCl4
Me2SnCl2
239
Sn-N(av)
Sn-X
231
230
227
226
255(av)
-
230
228
224
237(av)
-
257.73(6)
228(av)
256(av)
226(av)
255(av)
226.8(4)
244.59(13)
227(av)
240(av)
225(av)
252(av)
208(av)
Sn-C
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Table 2. 1J(119Sn,13C), 2J(119Sn,13C) and 2J(119Sn,19F) coupling constants of
pentafluoroethyl groups of stannanes.
For a structural characterization a crystal suitable for X ray
diffraction was grown by crystallization of the liquid inside a sealed
capillary in situ generating manually a crystal seed just under the
melting temperature at -47 °C and subsequently slowly chilling
down to -183 °C. (C2F5)3SnCp crystallizes in the monoclinic space
group P21/n and the molecular structure in the solid state confirms
a η1-coordination of the ring (Figure 2). Due to a fast sigmatropic
rearrangement, the 1H NMR spectrum of (C2F5)3SnCp shows only
one singlet at 6.4 ppm with a 2J(1H,117/119Sn) coupling constant of
34 Hz. The average C-Sn-C angle of the C2F5 groups (C1, C3,
C5) of 103° is significantly smaller than the average C-Sn-C angle
between the Cp carbon atom (C7) and the C2F5 groups (116°).
1J(119Sn,13C)/Hz
-394
2J(119Sn,13C)/Hz
2J(119Sn,19F)/Hz
-237
(C2F5)SnPh3
(C2F5)2SnMe2
(C2F5)2SnPh2
(C2F5)3SnCp
(C2F5)3SnPh
(C2F5)3SnBr
(C2F5)3SnCl
(C2F5)2SnBr2
55
62
-423
-264
-472
67
-273
-504
85
-324
-551
81
-323
-747
112
113
134
140
165
-450
-760
-460
-883
-525
(C2F5)2SnCl2
(C2F5)SnBr3
-973
-553
-1113
-625
1J(119Sn,13C)/Hz
Figure 2. Molecular structure of (C2F5)3SnCp; 50 % probability amplitude
displacement ellipsoids are shown; selected bond lengths [pm] and angles [°]:
Sn1-C1 220.4(2), Sn1-C3 221.7(2), Sn1-C5 221.2(2), Sn1-C7 214.8(2);
C1-Sn1-C3 106.86(7), C1-Sn1-C5 97.72(7), C5-Sn1-C3 103.28(8), C7-Sn1-C1
117.81(7), C7-Sn1-C3 116.39(7), C7-Sn1-C5 112.32(8).
-1500
-1000
-500
0
0
-100
-200
-300
-400
-500
-600
-700
R² = 0.992
The 19F NMR spectra of the tetracoordinated mono-, bis- and
tris(pentafluoroethyl)stannanes exhibit two separate resonances
for the CF3 and the CF2 units. The 19F resonances of the
hexacoordinated
1,10-phenanthroline
adducts
[(C2F5)3SnBr(phen)] and [(C2F5)3SnCl(phen)] show a spectrum of
higher order with two sets of signals for the C2F5 groups in the
ratio of 2:1. In general, the resonances of the CF3 (−79.9 to
−86.7 ppm) and the CF2 groups (−108.7 to −123.0 ppm) lie in a
narrow range and apparently are not depending on the
Figure 3. Correlation of 1J(119Sn,13C) and 2J(119Sn,19F) coupling constants of
(pentafluoroethyl)stannanes.
2
substitution pattern at the Sn center. However, the J(119Sn,19F)
coupling constants of the fluorine atoms of the CF2 groups of the
tetracoordinated stannanes are sensitive towards the electronic
character of the substituents. Whereas higher values are
observed for stannanes bearing electron withdrawing groups like
(C2F5)SnBr3 or (C2F5)2SnCl2, smaller constants are observed for
electron rich substituted stannanes such as (C2F5)SnPh3 and
(C2F5)2SnMe2 (see Table 2). A similar trend is observed for the
1J(119Sn,13C) and 2J(119Sn,13C) coupling constants. (C2F5)SnBr3
shows significant larger coupling constants than (C2F5)SnPh3
(see Table 2). The 2J(119Sn,19F) and the 1J(119Sn,13C) coupling
constants are strongly correlated. The correlation is depicted in
Figure 3 with a coefficient of determination of 0.992. A similar
correlation was observed by Eujen and Thurmann for
(trifluoromethyl)stannanes. Furthermore they determined the
signs of the 2J(119Sn,19F) and 1J(119Sn,13C) coupling constants
For the C2F5 derivatives the signs of the 2J(119Sn,19F) and the
1J(119Sn,13C) coupling constants were determined by 19F,13C and
19F,119Sn 2D NMR experiments. Figure
4
shows the
19F,13C HMQC (left) and 19F,119Sn HMQC (right) 2D NMR
1
correlation spectrum of (C2F5)2SnBr2. The values for the J(C,F)
coupling constant as well as for the reduced coupling constant
1K(C,F) are defined as negative (1J(C,F)
<
0).[17] The
19F,119Sn HMQC spectrum (right) shows a negative slope for the
line between the 13C satellites. In consequence, the reduced
coupling constants 1K(C,F) and 1K(C,Sn) (> 0) have opposite
signs. By the conversion to the 1J(13C,119Sn) coupling constant[17]
,
a negative sign (1J(13C,119Sn) < 0) is determined due to the
negative gyromagnetic ratio of tin and the positive gyromagnetic
ratio of carbon (gSn < 0, gC > 0). Taking into account that the
1J(13C,119Sn) coupling constant of (pentafluoroethyl)stannanes is
which are both negative[16]
.
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2
negative the sign of the J(119Sn,19F) can be determined by the
rise to
a
singlet at −9.9 ppm with tin satellites of
19F,13C HMQC spectrum (Figure 4 left). The tin satellites in this
spectrum show a positive slope, thus the reduced coupling
constants 1K(C,Sn) and 2K(Sn,F) exhibit the same sign (both > 0).
Hence, by the conversion to the 2J(119Sn,19F) coupling constant,
1J(13C,117/119Sn) = 367/385 Hz. The 13C{19F} NMR shows a singlet
at 120.2 ppm (2J(13C,117/119Sn) = 60/62 Hz) for the CF3 units and
a septet at 124.2 ppm (1J(13C,117/119Sn) = 404/423 Hz) for the
CF2 units with tin satellites. The sepet is caused by the long range
3J(13C,1H) coupling of 2 Hz to the methyl groups.
again a negative sign (2J(119Sn,19F) < 0) is determined due to the
negative gyromagnetic ratio of tin (gSn < 0) and the positive ratio
1
of fluorine (gF > 0). Consequently, the signs of the J(13C,119Sn)
and
the
2J(119Sn,19F)
coupling
as
constants
well as
of
of
the
the
(pentafluoroethyl)stannanes
(trifluoromethyl)stannanes are negative.[16]
Figure 5. 119Sn{19F} (top), 119Sn{1H} (middle) and 119Sn (bottom) NMR spectra
of (C2F5)2SnMe2.
Conclusions
Figure 4. Details of the 19F,13C HMQC (left) and 19F,119Sn HMQC (right) 2D
NMR correlation spectra of neat (C2F5)2SnBr2 for the determination of the sign
of the coupling constants.
LiC2F5 is an excellent transfer reagent for the introduction of
pentafluoroethyl groups in to chlorophenylstannanes, ClnSnPh4-n
,
to obtain (pentafluoroethyl)phenylstannanes, (C2F5)4-nSnPhn (n =
1-3), in good yields of 83 - 91 %.
These phenylstannanes react with gaseous hydrogen halides HX
(X = Cl, Br) to the corresponding (pentafluoroethyl)tin halides,
(C2F5)4-nSnXn (n = 1-3), in yields of 72 - 88 %. The reaction of
these organotin halides with the chelating ligand 1,10-
The 119Sn NMR spectra of tetracoordinated stannanes
reveal resonances from −33 to −335 ppm whereas the 119Sn
nuclei in the hexacoordinated phenanthroline adducts are more
shielded (−475 to −857 ppm).
In general, multinuclear NMR spectroscopy is an excellent tool for
the
characterization
of
(pentafluoroethyl)stannanes.
phenanthroline
(phen)
results
in
the
complexes
Dimethylbis(pentafluoroethyl)stannane, (C2F5)2SnMe2, could be
fully characterized by NMR spectroscopy because all elements in
this molecule have at least one isotope with a nuclear spin of
I = ½ and are therefore observable by NMR spectroscopy. The
1H NMR spectrum is characterized by a singlet at 0.74 ppm with
tin satellites (2J(1H,117/119Sn) = 62 Hz) demonstrating the bonding
to the tin atom. Two singlets are observed in the 19F NMR
spectrum at −83.3 ppm for the CF3 unit and at −118.2 ppm for the
CF2 unit with a 2J(19F,117/119Sn) coupling constant of 251/264 Hz.
The respective number of methyl and pentafluoroethyl
substituents is determined by the multiplicity in the 119Sn NMR
spectrum. The 119Sn{19F} NMR spectrum reveals a septet at
[(C2F5)4-nSnXn(phen)], which were characterized by single crystal
X-ray diffraction. The structural parameters reflect an increased
Lewis acidity of the (pentafluoroethyl)tin halides compared to
non-fluorinated
derivatives.
For
the
synthesis
of
methyl(pentafluoroethyl)stannanes the same procedure is applied.
The composition of (C2F5)2SnMe2 was completely deduced by
means of NMR spectroscopy. The (pentafluoroethyl)tin halides
are suited for further functionalization as for example shown by
the reaction with sodium cyclopentadienide yielding the
corresponding
(h1-cyclopentadienyl)tris(pentafluoroethyl)-
stannane (C2F5)2SnCp.
The development of an efficient protocol for the synthesis of
(pentafluoroethyl)stannanes opens the door to a rich area of tin
chemistry which is currently under investigation in our laboratory.
2
−33.2 ppm with a J(119Sn,1H) coupling constant of 63 Hz due to
the coupling to six hydrogen atoms (see Figure 5 top). The
119Sn{1H} NMR shows a quintet of septets due to the coupling to
four fluorine atoms of two CF2 units (2J(119Sn,19F) = 263 Hz) and
to the six fluorine atoms of two CF3 units (3J(119Sn,19F) = 3 Hz)
(see Figure 5 middle). Consequently, the non-decoupled 119Sn
NMR spectrum reveals a quintet of septets of septets (see Figure
5 bottom). In the 13C{1H} NMR spectrum the methyl groups give
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([D]chloroform, 298 K): δ=129.8 (s, J(C,Sn)=64 Hz; arom. C), 130.1 (s;
ipso-C), 131.5 (s, J(C,Sn)=14 Hz; arom. C), 136.8 ppm (s, J(C,Sn)=45 Hz;
arom. C); 13C{19F} NMR ([D]chloroform, 298 K): δ=120.3 (s,
2J(C,Sn)=65/67 Hz; CF3), 126.3 ppm (s, 1J(C,Sn)=450/472 Hz; CF2);
19F NMR ([D]chloroform, 298 K): δ=-113.8 (s, 2J(F,Sn)=262/273 Hz;
CF2), -82.5 ppm (s; CF3); 119Sn{1H} NMR ([D]chloroform, 298 K):
δ=-186.1 ppm (quin, 2J(F,Sn)=273 Hz); MS (EI, 20 eV) {m/z (%)
[assignment]}: 77.0 (18) [C6H5]+, 119.9 (5) [Sn]·+, 127.0 (31), 138.9 (13)
[SnF]+, 177.0 (15) [PhC2F4]+, 196.9 (22) [SnPh]+, 234.9 (9) [SnPhF2]+,
293.0 (100) [SnPh2F]+, 334.9 (5) [(C2F5)SnPhF]+, 393.0 (38)
Experimental Section
All chemicals were obtained from commercial sources and used without
further purification. Standard high vacuum techniques were employed
throughout all preparative procedures. Gas pressures in the range from
atmospheric pressure to 1 mbar were measured with the vacuubrand DVR
2, a piezo vacuum gauge. Nonvolatile compounds were handled in a dry
N2 atmosphere using Schlenk techniques.. The NMR spectra were
recorded on a Bruker Model Avance III 300 spectrometer (1H 300.13 MHz,
13C 75.47 MHz, 19F 282.40 MHz, 119Sn 111.9 MHz) with positive shifts
being downfield from the external standards (TMS (1H, 13C), CCl3F (19F),
~
[(C2F5)SnPh2]+, 434.9 (3) [(C2F5)2SnPh]+; IR (ATR): n=3076 (w), 1581 (w),
1487 (w), 1433 (w), 1314 (s), 1293 (m), 1188 (s), 1093 (s), 1070 (s), 1023
(w), 998 (w), 930 (s), 727 (s), 693 (s), 601 (w), 585 (w), 534 (w), 443 (m)
cm-1.
and SnMe4 (
119Sn)). The NMR spectra were recorded in the indicated
deuterated solvent or in relation to [D6]acetone filled capillaries. IR spectra
were recorded on an ALPHA-FT-IR spectrometer (Bruker). EI mass
spectra were recorded using an Autospec X magnetic sector mass
spectrometer with EBE geometry (Vacuum Generators, Manchester, UK)
equipped with a standard EI or CI source. Samples were introduced by
push rod in aluminium crucibles or by direct gas phase injection. Ions were
accelerated by 8 kV in EI mode. The crystal data were collected using
graphite-monochromated Mo-Ka radiation (l = 71.073 pm). The structures
were solved by Direct Methods and refined by full-matrix least-squares
cycles using SHELXS-97 and SHELXL-97 [18]. CCDC-1003536 (10),
CCDC-1003537(11), CCDC-1003538 (12), CCDC-1003539 (13), CCDC-
1003540 (14) and CCDC-1003541 (15) contain the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
(Pentafluoroethyl)triphenylstannane (3): Pentafluoroethyllithium was
generated as described for (1) from an n-butyllithium/n-hexane solution
(55 mL, c = 1.6 mol · L-1, 88 mmol) and pentafluoroethane (100 mmol) in
250 mL of diethyl ether. Chlorotriphenylstannane (30.5 g, 79.1 mmol),
dissolved in diethyl ether (20 mL), was added and the reaction mixture was
allowed to warm to ambient temperature (3 h). The resulting suspension
was filtered, and the filter cake was washed twice with 100 mL of diethyl
ether. All volatile compounds were removed under reduced pressure, the
residue was dissolved in toluene and filtered again. After removing all
volatile compounds under reduced pressure (C2F5)SnPh3 was obtained as
a colorless solid (33.9 g, 72.3 mmol, 91 %). 1H NMR ([D]chloroform,
298 K): δ=7.5-7.8 ppm (m; Ph); 13C{1H} NMR ([D]chloroform, 298 K):
δ=129.2 (s, J(C,Sn)=56/58 Hz; arom. C), 130.4 (s, J(C,Sn)=13 Hz; arom.
C), 133.7 (t, 3J(C,F)=2 Hz; ipso-C), 137.2 ppm (s, J(C,Sn)=40 Hz; arom.
C); 13C{19F} NMR ([D]chloroform, 298 K): δ=120.9 (s, 2J(C,Sn)=53/55 Hz;
CF3), 126.5 ppm (s, 1J(C,Sn)=376/394 Hz; CF2); 19F NMR ([D]chloroform,
298 K): δ=-116.4 (t, 3J(F,F)=1.9 Hz 2J(F,Sn)=227/237 Hz; CF2), -82.1 ppm
(t, 3J(F,F)=1.9 Hz; CF3); 119Sn{1H} NMR ([D]chloroform, 298 K):
δ=-149.7 ppm (t, m, 2J(F,Sn)=238 Hz); MS (EI, 20 eV) {m/z (%)
[assignment]}: 119.9 (7) [Sn]·+, 196.9 (19) [SnPh]+, 293.0 (3) [SnPh2F]+,
Tris(pentafluoroethyl)phenylstannane (1): An n-butyllithium/n-hexane
solution (70 mL, c = 1.6 mol · L-1, 112 mmol) was diluted with 300 mL of
diethyl ether, cooled to -78 °C, degassed and stirred under an atmosphere
of pentafluoroethane (125 mmol) for 20 min. Trichlorophenylstannane
(9.69 g, 32.1 mmol) was added and the reaction mixture was allowed to
warm to ambient temperature (3 h). The resulting suspension was filtered
and all volatile compounds were removed from the filtrate under reduced
pressure. The obtained crude product (16.1 g) was purified by vacuum
distillation (1∙10-6 bar, b.p.: 32 °C). (C2F5)3SnPh was obtained as a
colorless liquid (14.8 g, 26.8 mmol, 83 %). 1H NMR ([D]chloroform, 298 K):
d=7.5-7.7 ppm (m; Ph); 13C{1H} NMR ([D]chloroform, 298 K): δ=127.3 (s;
ipso-C), 130.2 (s, J(C,Sn)=71/74 Hz; arom. C), 132.5 (s, J(C,Sn)=16 Hz;
arom. C), 136.1 ppm (s, J(C,Sn)=49 Hz; arom. C); 13C{19F} NMR
([D]chloroform, 298 K): δ=119.4 (s, 2J(C,Sn)=77/81 Hz; CF3), 125.8 ppm
(s, 1J(C,Sn)=527/551 Hz; CF2); 19F NMR ([D]chloroform, 298 K): δ=-110.5
(s, 2J(F,Sn)=310/323 Hz; CF2), -82.9 ppm (s; CF3); 119Sn{1H} NMR
([D]chloroform, 298 K): δ=-234.1 ppm (sept, m, 2J(F,Sn)=324 Hz); MS (EI,
20 eV) {m/z (%) [assignment]}: 77.0 (95) [C6H5]+, 100.0 (59) [C2F4]·+, 119.9
(19) [Sn]·+, 127.0 (36), 138.9 (67) [SnF]+, 177.0 (38) [PhC2F4]+, 196.9 (39)
[SnPh]+, 215.9 (7) [SnPhF]·+, 234.9 (100) [SnPhF2]+, 334.9 (48)
~
351.0 (100) [SnPh3]+; IR (ATR): n=3071 (w), 2989 (w), 1581 (w), 1481 (m),
1430 (m), 1316 (s), 1292 (m), 1181 (s), 1089 (s), 1075 (s), 1048 (s), 1022
(m), 996 (m), 971 (w), 928 (s), 726 (s), 695 (s), 661 (m), 598 (w), 583 (w),
533 (w), 441(s) cm-1.
Dimethylbis(pentafluoroethyl)stannane (4): Pentafluoroethyllithium
was generated as described for (1) from an n-butyllithium/n-hexane
solution (43 mL, c = 1.6 mol · L-1, 69 mmol) and pentafluoroethane
(75 mmol) in 200 mL of diethyl ether. Dichlorodimethylstannane (5.27 g,
24.0 mmol), dissolved in diethyl ether (150 mL), was added and the
reaction mixture was allowed to warm to ambient temperature (3 h). The
resulting slurry was filtered and the solvents were removed from the filtrate
by an isotherm distillation at -60 °C. Fractional condensation yielded
(C2F5)2SnMe2 in the -60 °C cold trap as a colorless liquid (7.69 g,
19.9 mmol, 83 %, vapor pressure 15 mbar at 23 °C). 1H NMR
([D]chloroform, 298 K): δ=0.74 ppm (s, 2J(H,Sn)=62 Hz; CH3);
[(C2F5)SnPhF]+, 434.9 (25) [(C2F5)2SnPh]+; IR (ATR): n=3066 (w), 1540
(w), 1487 (w), 1436 (w), 1314 (s), 1294 (m), 1191 (s), 1084 (s), 1022 (w),
999 (w), 930 (s), 738 (m), 728 (m), 691 (m), 604 (w), 588 (w), 536 (w), 441
(m) cm-1.
~
13C{1H} NMR
([D]chloroform,
298 K):
δ=-9.9
ppm
(s,
1J(C,Sn)=367/385 Hz; CH3); 13C{19F} NMR ([D]chloroform, 298 K):
δ=120.2 (s, 2J(C,Sn)=60/62 Hz; CF3), 124.2 ppm (sept, 3J(C,H)=2 Hz,
1J(C,Sn)=404/423 Hz; CF2); 19F NMR ([D]chloroform, 298 K): δ =-118.8 (s,
2J(F,Sn)=251/264 Hz; CF2), -83.3 ppm (s; CF3); 119Sn{1H} NMR
([D]chloroform, 298 K): δ=-33.2 ppm (quin, sept, 2J(Sn,F)=263 Hz,
3J(Sn,F)=3 Hz);119Sn{19F} NMR ([D]chloroform, 298 K): δ=-33.2 ppm (sept,
2J(Sn,H)=63 Hz); 119Sn NMR ([D]chloroform, 298 K): δ =-33.2 ppm (quin,
sept, sept, 2J(Sn,F)=263 Hz, 2J(Sn,H)=63 Hz, 3J(Sn,F)=3 Hz); MS (EI,
20 eV) {m/z (%) [assignment]}: 69.0 (12), 100.0 (5) [C2F4]·+, 119.9 (9)
[Sn]·+, 134.9 (26) [SnCH3]+, 168.9 (100) [Sn(CH3)2F]+, 172.9 (41)
[SnCH3F2]+, 268.9 (13) [(C2F5)Sn(CH3)2]+, 272.9 (11) [(C2F5)SnCH3F]+; IR
Bis(pentafluoroethyl)diphenylstannane (2): Pentafluoroethyllithium
was generated as described for (1) from an n-butyllithium/n-hexane
solution (49 mL, c = 1.6 mol · L-1, 78 mmol) and pentafluoroethane
(94 mmol) in 250 mL of diethyl ether.
A
solution of
dichlorodiphenylstannane (11.3 g, 32.9 mmol) in diethyl ether (20 mL) was
added and the reaction mixture was allowed to warm to ambient
temperature (3 h). The resulting suspension was filtered and all volatile
compounds were removed under reduced pressure. The obtained crude
product (16.3 g) was purified by vacuum distillation (1∙10-6 bar, b.p.: 65 °C).
(C2F5)2SnPh2 was obtained as a colorless liquid (13.7 g, 26.8 mmol, 82 %).
1H NMR ([D]chloroform, 298 K): δ=7.3-7.7 ppm (m; Ph); 13C{1H} NMR
~
(gas phase): n=3011 (w), 2931 (w), 1538 (w), 1415 (w), 1323 (s), 1299 (m),
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1218 (s), 1202 (s), 1117 (s), 1087 (m), 1074 (m), 941 (m), 778 (w), 738
(m), 600 (w), 552 (w), 528 (w) cm-1.
Tribromo(pentafluoroethyl)stannane (9): Analogously to the protocol for
(5), the reaction of (pentafluoroethyl)triphenylstannane, (C2F5)SnPh3,
(15.66 g, 33.39 mmol) and gaseous hydrogen bromide (105 mmol) at
100 °C for 36 h gave the bromostannane (C2F5)SnBr3 as a colorless liquid
with a vapor pressure of 7 mbar at 22 °C (11.9 g, 24.9 mmol, 75 %).
13C{19F} NMR ([D]chloroform, 298 K): δ=118.7 (s, 2J(C,Sn)=157/165 Hz;
CF3), 119.1 ppm (s, 1J(C,Sn)=1064/1113 Hz, CF2); 19F NMR
([D]chloroform, 298 K): δ=-111.3 (q, 3J(F,F)=4 Hz, 2J(F,Sn)=598/625 Hz;
CF2), -79.9 ppm (t, 3J(F,F)=4 Hz, 3J(F,Sn)=23 Hz; CF3); 119Sn NMR
([D]chloroform, 298 K): δ=-335.3 ppm (t, 2J(F,Sn)=625 Hz); MS (EI, 20 eV)
{m/z (%) [assignment]}: 69.0 (13), 78.0 (28), 100.0 (63) [C2F4]·+, 119.0 (12)
[C2F5]+, 119.9 (12) [Sn]·+, 138.9 (14) [SnF]+, 198.8 (42) [SnBr]+, 277.7 (9)
[SnBr2]·+, 296.7 (12) [SnBr2F]+, 314.7 (21), 358.7 (100) [SnBr3]+, 396.7 (7)
Bromotris(pentafluoroethyl)stannane (5): Tris(pentafluoroethyl)phenyl-
stannane, (C2F5)3SnPh, (10.3 g, 18.6 mmol) and gaseous hydrogen
bromide (27.5 mmol) were loaded into a 500 mL ampoule with a Young
valve and stirred for 16 h at 130 °C. A fractional condensation yielded the
crude product in a -80 °C cooled trap contaminated with benzene.
Benzene was removed by an isothermal distillation to give the
bromostannane (C2F5)3SnBr as a colorless liquid with a vapor pressure of
15 mbar at 23 °C (9.1 g, 16.4 mmol, 88 %). 13C{19F} NMR ([D]chloroform,
298 K): δ=118.8 (s, 2J(C,Sn)=107/112 Hz; CF3), 123.9 ppm (s,
1J(C,Sn)=714/747 Hz; CF2); 19F NMR ([D]chloroform, 298 K): δ=-108.7 (s,
2J(F,Sn)=430/450 Hz; CF2), -81.7 ppm (s; CF3); 119Sn NMR ([D]chloroform,
298 K): δ=-240.0 ppm (sept, 2J(Sn,F=451 Hz); MS (EI, 20 eV) {m/z (%)
[assignment]}: 100.0 (82) [C2F4]·+, 119.0 (17) [C2F5]+, 119.9 (3) [Sn]·+,
138.9 (27) [SnF]+, 198.8 (42) [SnBr]+, 336.8 (100) [(C2F5)SnBrF]+, 376.9
~
[(C2F5)SnBr2]+; IR (gas phase): n=1322 (s), 1297 (m), 1223 (s), 1112 (s),
936 (s), 742 (m), 608 (w), 537 (w), 396 (w) cm-1.
Bromotris(pentafluoroethyl)-1,10-phenanthrolinetin(IV) (10): Bromo-
tris(pentafluoroethyl)stannane, (C2F5)3SnBr, (0.18 g, 0.32 mmol) was
condensed onto a solution of 1,10-phenanthroline (0.054 g, 0.30 mmol) in
3 mL of dichloromethane. After stirring for 30 h at ambient temperature all
volatile components were removed under reduced pressure. The 1,10-
phenanthroline complex [(C2F5)3SnBr(phen)] remained as a colorless
microcrystalline solid (0.22 g, 0.30 mmol, 100 %). Crystals suitable for
X-ray single crystal structure determination were grown from
dichloromethane solution at -25 °C. 1H NMR (dichloromethane/
~
(5) [(C2F5)2SnF]+, 436.8 (24) [(C2F5)2SnBr]+; IR (gas phase): n=1320 (s),
1299 (m), 1228 (s), 1119 (s), 939 (s), 742 (m) cm-1.
Chlorotris(pentafluoroethyl)stannane (6): Analogously to the protocol
for (5), tris(pentafluoroethyl)phenylstannane, (C2F5)3SnPh, (14.4 g,
26.0 mmol) and gaseous hydrogen chloride (35.0 mmol) were combined
at 170 °C for 72 h to afford the chlorostannane (C2F5)3SnCl as a colorless
liquid with a vapor pressure of 25 mbar at 23 °C (10.9 g, 21.3 mmol, 82 %).
13C{19F} NMR ([D]chloroform, 298 K): δ=118.6 (s, 2J(C,Sn)=108/113 Hz;
CF3), 125.2 ppm (s, 1J(C,Sn)=727/760 Hz; CF2); 19F NMR ([D]chloroform,
298 K): δ=-108.7 (s, 2J(F,Sn)=441/460 Hz; CF2), -82.0 ppm (s; CF3);
119Sn NMR ([D]chloroform, 298 K): δ=-206.9 ppm (sept, 2J(Sn,F)=462 Hz);
MS (EI, 20 eV) {m/z (%) [assignment]}: 100.0 (100) [C2F4]·+, 119.0 (17)
[C2F5]+, 119.9 (3) [Sn]·+, 138.9 (26) [SnF]+, 154.9 (33) [SnCl]+, 276.9 (5)
[(C2F5)SnF2]+, 292.9 (43) [(C2F5)SnClF]+, 376.9 (10) [(C2F5)2SnF]+, 392.9
[D6]acetone,
298 K):
δ=8.07/8.08
(2
dd,
3J(H3,H4)=8.1 Hz,
3J(H3,H2)=5.1 Hz, 3J(H8,H7)=8.1 Hz, 3J(H8,H9)=5.1 Hz, 2H; H3/H8), 8.11
(s, 2H; H5/H6), 8.75/8.78 (2 dd, 3J(H4,H3)=8.2 Hz, 4J(H4,H2)=1.5 Hz,
3J(H7,H8)=8.2 Hz, 4J(H7,H9)=1.5 Hz, 2H; H4/H7), 9.28/9.80 ppm (2 d,
3J(H2,H3)=5.1 Hz, 3J(H9,H8)=5.1 Hz, 2H; H2/H9); 13C{1H} NMR (dichloro-
methane/[D6]acetone, 298 K): δ=125.4/125.7 (2 s; C3/8), 127.6/127.7 (2 s;
C5/6), 129.7/129.9 (2 s, C4a/C6a), 137.6/138.6 (2 s; C11/12), 141.9/142.2
(2 s, C4/7), 149.0/149.1 ppm (s; t, 4J(C,F)=6 Hz; C2/9); 13C{19F} NMR
(dichloromethane/[D6]acetone, 298 K): δ=120.2 (s, 2J(C,Sn)=83/87 Hz;
CF3), 120.2 (s, 2J(C,Sn)=144/150 Hz; 2 CF3), 126.1 (s; CF2), 129.0 ppm
(s; 2 CF2); 19F NMR (dichloromethane/[D6]acetone, 298 K): δ=-117.8 (m,
4F; CF2), -112.1 (m, 2J(F,Sn)=330 Hz, 2F; CF2), -81.8 (m, 6F;
CF3), -81.2 ppm (m, 3F; CF3); 119Sn{1H} NMR (dichloromethane/
~
(10) [(C2F5)2SnCl]+; IR (gas phase): n=1320 (s), 1299 (m), 1230 (s), 1120
(s), 940 (s), 742 (m) cm-1.
Dibromobis(pentafluoroethyl)stannane (7): Analogously to the protocol
for (5) bis(pentafluoroethyl)diphenylstannane, (C2F5)2SnPh2, (26.5 g,
51.9 mmol) and gaseous hydrogen bromide (120 mmol) were reacted at
100 °C for 16 h to yield the bromostannane (C2F5)2SnBr2 as a colorless
liquid with a vapor pressure of 20 mbar at 23 °C (23.1 g, 44.7 mmol, 86 %).
13C{19F} NMR ([D]chloroform, 298 K): δ=118.8 (s, 2J(C,Sn)=128/134 Hz;
CF3), 122.0 ppm (s, 1J(C,Sn)=843/883 Hz; CF2); 19F NMR ([D]chloroform,
298 K): δ=-110.0 (s, 2J(F,Sn)=502/525 Hz; CF2), -80.7 ppm (s; CF3);
119Sn NMR ([D]chloroform, 298 K): δ=-232.3 ppm (quin, 2J(Sn,F)=524 Hz);
MS (EI, 20 eV) {m/z (%) [assignment]}: 100.0 (89) [C2F4]·+, 119.0 (30)
[C2F5]+, 119.9 (10) [Sn]·+, 138.9 (30) [SnF]+, 198.8 (40) [SnBr]+, 277.7 (16)
[SnBr2]·+, 296.7 (92) [SnBr2F]+, 336.8 (8) [(C2F5)SnBrF]+, 396.7 (100)
~
[D6]acetone, 298 K): δ=-515.1 ppm (m); IR (ATR): n=2961 (w), 2923 (w),
2852 (w), 1633 (w), 1591 (w), 1527 (m), 1498 (w), 1457 (w), 1434 (m),
1298 (s), 1278 (m), 1232 (w), 1196 (s), 1172 (s), 1151 (s), 1109 (m), 1074
(s), 1051 (s), 965 (w), 915 (s), 868 (m), 847 (s), 801 (m), 776 (w), 730 (s),
721 (s), 648 (w), 599 (w), 585 (w), 532 (w), 443 (w), 423 (m) cm-1.
Chlorotris(pentafluoroethyl)-1,10-phenanthrolinetin(IV) (11): Chloro-
tris(pentafluoroethyl)stannane, (C2F5)3SnCl, (0.54 g, 1.1 mmol) was
condensed onto a solution of 1,10-phenanthroline (0.19 g, 1.1 mmol) in
3 mL of dichloromethane. After stirring for 30 h at ambient temperature all
volatile components were removed under reduced pressure to give the
~
[(C2F5)SnBr2]+; IR (gas phase): n=1320 (s), 1297 (m), 1226 (s), 1118 (s),
938 (s), 742 (m) cm-1.
1,10-phenanthroline complex [(C2F5)3SnCl(phen)] as
a
colorless
microcrystalline solid (0.62 g, 0.90 mmol, 82 %). Crystals suitable for X-
ray single crystal structure determination were grown from
dichloromethane solution at -25 °C. 1H NMR (dichloromethane/
[D6]acetone, 298 K): δ=8.10 (m, 2H; H3/8), 8.12 (s, 2H; H5/6), 8.76/8.80
(2 d, 3J(H4,H3)=8.7 Hz, 3J(H7,H8)=8.7 Hz, 2H; H4/7), 9.27/9.69 ppm (2 d,
3J(H2,H3)=4.8 Hz, 3J(H9,H8)=4.8 Hz, 2H; H2/H9); 13C{1H} NMR
(dichloromethane/ [D6]acetone, 298 K): δ=125.6/125.8 (2 s; C3/C8),
127.5/127.8 (2 s; C5/6), 129.6/129.9 (2 s; C4a/C6a), 137.7/138.6 (2 s;
C11/12), 141.8/142.2 (2 s; C3/C8), 148.8/149.0 ppm (s; t, 4J(C,F)=6 Hz;
C2/C9); 13C{19F} NMR (dichloromethane/[D6]acetone, 298 K): δ=120.3 (s,
2J(C,Sn)=84/87 Hz; CF3), 120.4 (s, 2J(C,Sn)=141/149 Hz; 2 CF3), 126.9 (s;
CF2), 129.7 ppm (s; CF2); 19F NMR (dichloromethane/[D6]acetone, 298 K):
δ=-118.1 (m, 4F; CF2), -112.6 (m, 2J(F,Sn)=340 Hz, 2F; CF2), -82.0 (m,
6F; CF3), -81.7 ppm (m, 3F; CF3); 119Sn{1H} NMR (dichloromethane/
Dichlorobis(pentafluoroethyl)stannane (8): Analogously to the protocol
for (5) bis(pentafluoroethyl)diphenylstannane, (C2F5)2SnPh2, (5.76 g,
11.3 mmol) and gaseous hydrogen chloride (26 mmol) reacted at 75 °C for
16 h to furnish the chlorostannane (C2F5)2SnCl2 as a colorless liquid with
a vapor pressure of 50 mbar at 23 °C (3.48 g, 8.14 mmol, 72 %).
13C{19F} NMR ([D]chloroform, 298 K): δ=118.7 (s, 2J(C,Sn)=134/140 Hz;
CF3), 124.8 ppm (s, 1J(C,Sn)=931/973 Hz; CF2); 19F NMR ([D]chloroform,
298 K): δ=-109.8 (s, 2J(F,Sn)=529/553 Hz; CF2), -81.4 ppm (s; CF3);
119Sn NMR ([D]chloroform, 298 K): δ=-141.2 ppm (quin, 2J(F,Sn)=554 Hz);
MS (EI, 20 eV) {m/z (%) [assignment]}: 100.0 (100) [C2F4]·+, 119.0 (23)
[C2F5]+, 138.9 (10) [SnF]+, 154.9 (22) [SnCl]+, 208.8 (31) [SnCl2F]+, 292.9
~
(6) [(C2F5)SnClF]+, 308.8 (20) [(C2F5)SnCl2]+; IR (gas phase): n=1322 (s),
1299 (m), 1227 (s), 1120 (s), 939 (s), 743 (m), 608 (w), 402 (m) cm-1.
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~
[D6]acetone, 298 K): δ=-489.9 ppm (m); IR (ATR): n=3039 (w), 1632 (w),
1589 (w), 1527 (m), 1499 (w), 1434 (m), 1353 (w), 1302 (s), 1280 (m),
1196 (s), 1173 (s), 1151 (s), 1109 (m), 1077 (s), 1051 (s), 967 (w), 917 (s),
869 (w), 847 (s), 805 (w), 776 (w), 763 (w), 731 (s), 722 (s), 670 (w), 649
(w), 620 (w), 599 (w), 586 (w), 533 (w), 480 (w), 443 (w), 424 (m) cm-1.
(broad), 3J(H4,H3)=8.2 Hz, 2H; H4/7), 10.32 ppm (d (broad),
3J(H2,H3)=5.2 Hz, 2H; H2/9); 13C{1H} NMR (DMF/[D6]acetone, 298 K):
δ=127.3 (s, 3J(Sn,C)=7 Hz; C3/8), 128.8 (s; C5/6), 130.7 (s; C4a/6a),
135.0 (s, 2J(C,Sn)=15 Hz; C11/12), 144.3 (s; C4/7), 147.5 ppm (s,
2J(C,Sn)=12 Hz, C2/9); 13C{19F} NMR (DMF/[D6]acetone, 298 K): δ=120.7
(s, 2J(C,Sn)=167/174 Hz, CF3), 123.4 ppm (s, 1J(C,Sn)=1303/1362 Hz;
CF2);
19F NMR
(DMF/[D6]acetone,
298 K):
δ=-120.7
(s,
Dibromobis(pentafluoroethyl)-1,10-phenanthrolinetin(IV) (12):
bromobis(pentafluoroethyl)stannane, (C2F5)2SnBr2, (0.21 g, 0.41 mmol)
was condensed onto solution of 1,10-phenanthroline (0.054 g,
0.30 mmol) in 3 mL of dichloromethane. After stirring for 30 h all volatile
components were removed under reduced pressure to give the 1,10-
Di-
2J(F,Sn)=567/593 Hz, 2F; CF2), -80.5 ppm (s, 3J(F,Sn)=16 Hz, 3F, CF3);
119Sn{1H} NMR (DMF/[D6]acetone, 298 K): δ=-856.5 (t (broad),
2J(Sn,F)=595 Hz); IR(ATR): n=3080 (w), 2922 (w), 2853 (w), 1629 (w),
a
~
1609 (w), 1588 (w), 1523 (m), 1495 (w), 1430 (s), 1343 (w), 1321 (w), 1298
(m), 1277 (w), 1225 (w), 1205 (s), 1176 (s), 1150 (m), 1105 (m), 1081 (s),
1051 (s), 969 (w), 916 (s), 869 (w), 847 (s), 778 (w), 735 (m), 726 (m), 717
(s), 650 (m), 600 (w), 582 (w), 559 (w), 543 (w), 532 (w), 510 (w), 483 (w),
445 (w), 425 (m) cm-1.
phenanthroline
complex
[(C2F5)2SnBr2(phen)]
as
a
colorless
microcrystalline solid (0.21 g, 0.30 mmol, 100 %). Crystals suitable for
X-ray single crystal structure determination were grown from
dichloromethane solution at -25 °C. 1H NMR (dichloromethane/
[D6]acetone, 298 K): δ=8.15 (d, d, 3J(H3,H4)=8.2 Hz, 3J(H3,H2)=5.1 Hz,
2H; H3/H8), 8.17 (s, 2H; H5/H6), 8.82 (d, d, 3J(H4,H3)=8.2 Hz,
4J(H4,H2)=1.4 Hz, 2H; H4/H7), 9.83 ppm (d, 3J(H2,H3)=5.1 Hz, 2H;
H2/H9); 13C{1H} NMR (dichloromethane/ [D6]acetone, 298 K): δ=125.8 (s;
C3/C8), 127.6 (s; C5/C6), 129.6 (s; C4a/C6a), 138.2 (s; C11/C12), 142.2
(s; C4/C7), 149.4 ppm (s; C2/C9); 13C{19F} NMR (dichloromethane/
[D6]acetone, 298 K): δ=120.2 (s; CF3), 123.1 ppm (s; CF2); 19F NMR
(dichloromethane/[D6]acetone, 298 K): δ=-118.7 (s, 2J(F,Sn)=602/629 Hz,
4F; CF2), -80.6 ppm (s, 3J(F,Sn)=23 Hz, 6F; CF3); 119Sn{1H} NMR
(dichloromethane/[D6]acetone, 298 K): δ=-539.8 ppm (m); IR (ATR):
(η1-Cyclopentadienyl)tris(pentafluoroethyl)stannane (15): Sodium
cyclopentadienide
(123 mg,
1.41 mmol)
and
a
sample
of
bromotris(pentafluoroethyl)stannane (754 mg, 1.36 mmol) were loaded
into a Young valve ampoule. After stirring at ambient temperature for 1 d
highly volatile compounds were removed in
a static vacuum. By
condensation at ambient temperature and 1·10-3 mbar (C2F5)3SnCp was
obtained as a yellow oil (0.56 g, 1.0 mmol, 76 %). 1H NMR ([D]chloroform,
298 K): δ=6.39 ppm (s, 2J(H,Sn)=34 Hz; C5H5); 13C{1H} NMR
([D]chloroform, 298 K): δ=115.0 ppm (s, 1J(C,Sn)=41 Hz; C5H5);
13C{19F} NMR: δ=119.5 (s, 2J(C,Sn)=81/85 Hz; CF3), 126.0 ppm (s,
1J(C,Sn)=482/504 Hz; CF2); 19F NMR ([D]chloroform, 298 K): δ=-110.1 (s,
2J(F,Sn)=310/324 Hz; CF2), -83.1 ppm (s; CF3); 119Sn{19F} NMR
~
n= 3081 (w), 2962 (w), 1630 (w), 1588 (w), 1524 (m), 1494 (w), 1430 (m),
1345 (w), 1304 (s), 1280 (w), 1260 (w), 1177 (s), 1146 (m), 1086 (s), 1058
(s), 973 (w), 918 (s), 867 (m), 846 (s), 801 (m), 733 (s), 720 (s), 648 (w),
603 (w), 585 (w), 558 (w), 532 (w), 482 (w), 442 (w), 422 (m) cm-1.
([D]chloroform,
298 K):
δ =-203.8 ppm
(sext,
2J(Sn,H)=35 Hz);
119Sn{1H} NMR ([D]chloroform, 298 K): δ=-203.8 ppm (sept, dec,
2J(F,Sn)=324 Hz, 3J(F,Sn)=4 Hz); MS (EI, 70 eV.) {m/z (%) [assignment]}:
49.0 (40), 51.0 (14), 65.0 (20) [Cp]+, 84.0 (27) [CpF]·+, 85.9 (18), 100.0 (5)
[C2F4]·+, 127.0 (13), 138.9 (8) [SnF]+, 184.9 (100) [SnCp]+, 222.9 (11)
[SnF2Cp]+, 322.9 (6) [(C2F5)SnFCp]+, 422.9 (11) [(C2F5)2SnCp]+, 541.9 (4)
Dichlorobis(pentafluoroethyl)-1,10-phenanthrolinetin(IV) (13):
Di-
chlorobis(pentafluoroethyl)stannane, (C2F5)2SnCl2, (0.52 g, 1.2 mmol) was
condensed onto a solution of 1,10-phenanthroline (0.20 g, 1.1 mmol) in
3 mL of dichloromethane. After stirring for 16 hours all volatile components
were removed under reduced pressure and the 1,10-phenanthroline
complex [(C2F5)2SnCl2(phen)] remained as a colorless microcrystalline
solid (0.66 g, 1.09 mmol, 99 %). Crystals suitable for X-ray single crystal
structure determination were grown from acetonitrile solution at -25 °C. 1H
NMR (acetonitrile/[D6]acetone, 298 K): δ=9.00 (m, 2H; H3/H8), 9.03 (s, 2H;
H5/H6), 9.76 (d (broad), 3J(H4,H3)=8.2 Hz, 2H; H4/H9), 10.39 ppm (d
(broad), 3J(H2,H3)=5.0 Hz, 2H; H2/H9); 13C{1H} NMR (acetonitrile/
[D6]acetone, 298 K): δ=127.2 (s; C3/C8), 128.7 (s; C5/C6), 130.6 (s;
C4a/C6a), 138.4 (s; C11/C12), 144.1 (s; C4/C7), 149.7 ppm (s; C2/C9);
~
[(C2F5)3SnCp].+; IR (ATR): n=1464 (w), 1384 (w), 1312 (s), 1293 (m), 1191
(s), 1088 (s), 1022 (w), 982 (w), 928 (s), 908 (m), 816 (w), 755 (s), 738 (s),
648 (m), 603 (m), 587 (w), 560 (w), 535 (w), 430 (w) cm-1.
13C{19F} NMR
2J(C,Sn)=174/182 Hz; CF3), 126.3 ppm (s, 1J(C,Sn)=1614/1690 Hz; CF2);
(acetonitrile/[D6]acetone,
298 K):
δ=121.2
(s,
19F
NMR
(acetonitrile/[D6]acetone,
298 K):
δ=-119.3
(s,
2J(F,Sn)=581/608 Hz, 4F; CF2), -81.0 ppm (s, 3J(F,Sn)=24 Hz, 6F; CF3);
119Sn{1H} NMR (acetonitrile/[D6]acetone, 298 K): δ=-474.8 ppm (quin
(broad), 2J(Sn,F)=614 Hz); IR (ATR): n=3085 (w), 1631 (w), 1608 (w),
~
1588 (w), 1524 (w), 1494 (m), 1430 (m), 1345 (w), 1307 (s), 1285 (m),
1177 (s), 1148 (m), 1088 (s), 1058 (s), 957 (w), 923 (s), 868 (m), 848 (s),
778 (w), 734 (m), 721 (s), 650 (w), 603 (w), 585 (w), 558 (w), 533 (w), 482
(w), 443 (w), 423 (m) cm-1.
Tribromo(pentafluoroethyl)-1,10-phenanthrolinetin(IV) (14):
Tribromopentafluoroethylstannane, (C2F5)SnBr3, (0.48 g, 1.0 mmol) was
condensed onto a solution of 1,10-phenanthroline (0.18 g, 1.0 mmol)
dissolved in 3 mL of acetonitrile. It was heated until the white precipitate
dissolved. All volatile components were removed under reduced pressure
and the 1,10-phenanthroline complex [(C2F5)SnBr3(phen)] remained as a
colorless microcrystalline solid (0.44 g, 0.67 mmol, 67 %). Crystals
suitable for X-ray single crystal structure determination were grown from a
hot acetonitrile solution. 1H NMR (DMF/[D6]acetone, 298 K): δ=8.96 (s, 2H;
H5/6), 8.98 (d, d, 3J(H3,H4)=8.2 Hz, 3J(H3,H2)=5.2 Hz, 2H; H3/8), 9.75 (d
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10.1002/chem.201701270
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Table 3. Crystal data and refinement characteristics for [(C2F5)3SnBr(phen)], [(C2F5)2SnBr2(phen)], [(C2F5)3SnCl(phen)], [(C2F5)2SnCl2(phen)], [(C2F5)SnBr3(phen)]
and (C2F5)3SnCp.
[(C2F5)3SnBr(phen)]a [(C2F5)2SnBr2(phen)] [(C2F5)3SnCl(phen)]b [(C2F5)2SnCl2(phen)] [(C2F5)SnBr3(phen)]
(C2F5)3SnCp
10
12
11
13
14
15
Crystallographic Section
C18H8ClF15N2Sn
1328
empirical formula
F(000)
C18H8BrF15N2Sn
1400
C16H8Br2F10N2Sn
2624
C16H8Cl2F10N2Sn
2336
C14H8Br3F5N2Sn
1224
C11H5F15Sn
1024
895.36(2)
1368.17 (2)
1305.74(2)
90
a / pm
988.99(2)
1010.56(2)
2297.20(6)
90
1625.1(1)
1498.6(3)
1649.8(2)
90
988.03(2)
1005.95(2)
2290.71(6)
90
1612.33(2)
1469.47(2)
1626.26(3)
90
896.41(1)
1195.00(2)
1634.84(3)
90
b / pm
c / pm
a / °
91.938(2)
90
b / °
98.254(1)
90
90
98.236(2)
90
90
90.835(1)
90
g / °
90
90
V / 106 · Å3
2272.11(9)
4
4017.9(8)
8
2253.28(9)
4
3853.05(10)
8
1751.07(5)
4
1598.63(4)
4
Z
ρ / g·cm-3
crystal system
space group
shape / color
crystal size/ mm3
2.151
2.304
2.038
2.096
2.495
2.247
monoclinic
P21/n
orthorhombic
Pbca
monoclinic
P21/n
orthorhombic
Pbca
monoclinic
P21/n
monoclinic
P21/n
colorless fragment
0.30 x 0.20 x 0.10
colorless column
0.30 x 0.10 x 0.10
colorless fragment
0.30 x 0.29 x 0.07
Data collection
Kappa CCD
100(2)
colorless fragment
0.30 x 0.24 x 0.04
colorless fragment
0.30 x 0.25 x 0.25
colorless cylindrically
0.3 × 0.2 × 0.2
diffractometer
T / K
SuperNova
90.0(1)
100(2)
100(2)
100(2)
100(2)
theta range [°]
2.94 / 27.48
3.08 / 30.00
2.95 / 27.48
3.13 / 30.00
3.41 / 30.00
2.72 to 30.03
-12<=h<=12
-12<=h<=12
-13<=k<=13
-29<=l<=29
-22<=h<=22
-21<=k<=21
-23<=l<=22
-12<=h<=12
-13<=k<=13
-29<=l<=29
-22<=h<=22
-20<=k<=20
-22<=l<=22
-12<=h<=12
-16<=k<=16
-22<=l<=22
index range
-19<=k<=19
-18<=l<=18
total data collected
unique data
34985
5189
85908
5849
9991
5157
91422
5597
40873
5096
101043
4675
observed data (I > 2s)
R(int) / R(s)
4619
4648
4239
4948
4380
4539
0.049
0.0867
0.0259
0.060
0.084
0.0400
µ / mm-1
3.016
5.347
1.387
1.704
8.354
1.755
R1 / wR2 [I>2s(I)]
R1 / wR2 (all data)
goodness of fit (Sall)
Drmax/min / e Å-3
CCDC number
0.0427 / 0.0943
0.0502 / 0.0971
1.131
0.0314 / 0.0606
0.0502 / 0.0671
1.078
0.0429 / 0.0879
0.0563 / 0.0927
1.068
0.0404 / 0.1040
0.0455 / 0.1070
1.104
0.0414 / 0.1113
0.0498 / 0.1159
1.061
0.0239 / 0.0522
0.0250 / 0.0527
1.205
3.625 / -1.928
1003536
1.001 / -0.771
1003538
3.622 / -1.989
1003537
4.371 / -1.361
1003539
1.317 / -1.535
10035340
1.08/-0.38
1003540
a
Compound 10 shows a disorder of the bromine with on C2F5 ligand in ratio 89:11; b Compound 11 shows a disorder of the chlorine with on C2F5 ligand in ratio
90:10.
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This work was financially supported by Merck KGaA (Darmstadt,
Germany) and Solvay (Hannover, Germany) which is gratefully
acknowledged. We acknowledge the support by the Deutsche
Forschungsgemeinschaft (Core Facility GED@BI, Mi477/21-1)
and we thank Prof. Dr. Lothar Weber and Dr. Julia Bader for
helpful discussions.
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FULL PAPER
Johannes Klösener, Markus
Wiesemann, Mark Niemann, Beate
Neumann, Hans-Georg Stammler and
Berthold Hoge*
Page No. – Page No.
Synthesis of Mono-, Bis- and
Tris(pentafluoroethyl)tin Derivatives,
(C2F5)4−nSnXn (X = Ph, Me, Cl, Br, Cp;
n = 1-3)
In this contribution, we present a convenient protocol for the high yield synthesis of
(pentafluoroethyl)stannanes (n = 1-3) by using LiC2F5. (Pentafluoroethyl)phenyl-
stannanes are functionalized by gaseous hydrogen halides HX (X = Cl, Br) to give
(pentafluoroethyl)tin halides, their corresponding 1,10-phenanthroline (phen)
complexes were structurally characterized by X-ray diffraction analysis.
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