The Tris(pentafluoroethyl)stannate(II) Anion, [Sn(C2F5)3]?—Synthesis and Reactivity

Article abstract of DOI:10.1002/chem.201702855

Syntheses of salts containing the tris(pentafluoroethyl)stannate(II) ion, [Sn(C₂F₅)₃]^?, were achieved through deprotonation of the corresponding stannane, HSn(C₂F₅)₃, as well as

Full text of DOI:10.1002/chem.201702855

A Journal of
Accepted Article
Title: The Tris(pentafluoroethyl)stannate(II) Anion [Sn(C2F5)3]- -
Synthesis and Reactivity
Authors: Markus Wiesemann, Johannes Klösener, Mark Niemann,
Beate Neumann, Hans-Georg Stammler, and Berthold Hoge
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To be cited as: Chem. Eur. J. 10.1002/chem.201702855
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-
The Tris(pentafluoroethyl)stannate(II) Anion, [Sn(C F ) ] –
2
5 3
Synthesis and Reactivity
Markus Wiesemann, Johannes Klösener, Mark Niemann, Beate Neumann, Hans-Georg Stammler and
Berthold Hoge*
[
8]
Abstract:
tris(pentafluoroethyl)stannate(II) ion, [Sn(C
deprotonation of the corresponding stannane, HSn(C
by direct pentafluoroethylation of SnCl with LiC
Syntheses
of
salts
containing
the
apparent. The replacement of electron donating alkyl by
electron withdrawing perfluoroalkyl groups exerts a dramatic
effect on the electronic nature of organotin compounds due to the
-
2
F ) ] , were achieved via
5 3
2
5
F
5
)
3
, as well as
2
2
F
. The electron
stabilization of the negative charge. Using LiC
generated by the combination of n-butyllithium with
pentafluoroethane, as group transfer reagent,
2 5
F , which is
withdrawing substituents have substantial influence on the stability
and reactivity of the anion as documented by its treatment with main
group halides. Alkyl halides (R-X) underwent nucleophilic
a
2 5
C F
[
9]
pentafluoroethyltin compounds are conveniently accessible.
substitutions to afford RSn(C
2 5 3
F ) , whereas Si, Ge, Sn, P halides gave
-
rise to oxidation processes yielding hypervalent [SnX
2
(C
Cl, Br, I). Moreover the unsymmetrical distannane, n-
SnSn(C , was disclosed as an alternative precursor for the
moiety. Whereas neither the solid state structure nor its
2 5 3
F ) ] salts (X
=
Results and Discussion
Bu
3
2 5 3
F )
2 5 3
Sn(C F )
We recently published the synthesis of tris(pentafluoroethyl)tin
halides, X Sn(C 4-n (X = Cl, Br; n = 1-3), by dearylation of the
phenyl protected derivatives using gaseous HBr or HCl,
spectra in alkane solution reveal unexpected peculiarities, unusual
dissociation of the compound in coordinating solvents into
n
2 5
F )
+
-
[
10]
[
3 n 2 5 3
Bu Sn(D) ] and [Sn(C F ) ] ions was observed.
respectively.
further derivatization. The reaction of BrSn(C
hydride leads to the formation of tris(pentafluoroethyl)stannane,
HSn(C , (Scheme 1). This compound features an uncommon
The introduction of halide functionalities allows
2
5 3
F )
with tributyltin
2
5 3
F )
Introduction
polarization of the tin hydrogen bond indebted to the electron
withdrawing pentafluoroethyl groups, with the result of an acidic
character of the Sn-H unit. The effect of an increased acidity by
the introduction of electron withdrawing groups is known for main
3
Since the first synthesis of a trialkylstannate(II), NaSnMe , by
Kraus et al. in 1922, and pioneering work in the field of stannyl
lithium derivatives in the 1950’s, these reactive species were
utilized for the construction of various functional polymers,
group elements. Finze et al. impressively demonstrates that even
-
the anionic hydridoborate anion [HB(CN)
3
] is deprotonated in the
[
1,2]
pharmaceuticals, and agrochemicals.
In addition stannyl
reaction with strong bases like lithiumdiisopropylamide (LDA) or
lithium compounds were employed for the synthesis of a variety
of stannanes, which were appropriate for further derivatization via
[11]
tBuLi.
An increased acidity was also found for the
pentafluoroethyl-silicon and germanium
compounds. Solvation of HSn(C in pure water leads to a
complete deprotonation and formation of the
corresponding
[
3]
palladium-catalyzed couplings.
Their preparation was commonly accomplished by the
[12]
2
5 3
F )
the
[
2]
treatment of tin(II) chloride with organolithiums , the reduction of
tris(pentafluoroethyl)stannate anion which was proven by multi-
nuclear NMR spectroscopy (compare SI). Titration with NaOH in
[
4]
triorganotin chlorides or distannanes with elemental lithium or
the deprotonation of hydridostannanes with strong bases like
aqueous isopropanol solution leads to a pK
a
value of 0.8
[
5]
LDA. In most cases methyl-, phenyl- or n-butyl-tin compounds
were considered. But in spite of thorough work and various
protocols the selective synthesis of such species remained
challenging due to by-product formation, low yields or prolonged
emphasizing the distinct effect of the perfluorinated substituents
on the nature of the Sn-H bond (Figure 1).
[
6]
reaction times. Therefore, the improvement of stannyl lithium
synthesis, for example by naphthalene catalyzed reduction, is still
[
7]
an issue of current research.
Beside stannyl lithium compounds free stannate anions are
accessible via complexation of alkali metals with crown ether.
3
Thus, in [K(18-crown-6)][SnPh ] no significant interionic contact is
*
M. Wiesemann, Dr. J. Klösener, M. Niemann, B. Neumann, Dr. H.-
G. Stammler, Prof. Dr. B. Hoge
Centrum für Molekulare Materialien
2 5 3
Scheme 1. HSn(C F ) formation and subsequent deprotonation with water.
Fakultät für Chemie, Universität Bielefeld,
Universitätsstraße 25, 33615 Bielefeld (Germany)
E-Mail: b.hoge@uni-bielefeld.de
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Although the [HBDMAN][Sn(C
2
F
5
)
3
] is reasonably stable, its
synthesis is not straightforward. The preparation of the precursor
BrSn(C requires a multi-step protocol, and the liberation of
an equimolar amount of hazardous n-Bu SnBr prevented a broad
2
5 3
F )
3
application and upscaling. A more direct procedure for these
stannates was highly desirable. Tin(II) chloride selectively reacts
with LiC
smoothly converted into
tetraphenylphosphonium derivative by combination with [PPh
Scheme 2).
2
F
5
furnishing the thermolabile LiSn(C
stable and analytically pure
]Cl
2 5 3
F ) , which was
a
4
(
Figure 1. Titration curve of HSn(C
water) with aqueous isopropanolic NaOH (0.006 M). It was assumed that the
pK value of 0.8 in this media corresponds to the half equivalence point at
4.03 mL/0.8) and that the equivalence point matches the point of the maximum
2 5 3
F ) in aqueous isopropanol (10 mL, 0.5 %
a
(
gradient ∂pH/∂V.
-
2 5 3
Scheme 2. Synthesis of [Sn(C F ) ] salts.
In order to obtain further structural data the stannane was also
deprotonated by 1,8-bis(dimethylamino)naphthalene (BDMAN)
leading to the corresponding tris(pentafluoroethyl)stannate(II)
salt. The product crystallizes from dichloromethane solution in the
1
9
In the F NMR spectrum of this tin(II) compound the resonance
2
2
for the CF groups at -117.5 ppm exhibits a diagnostic J(F,Sn)
coupling constant of 117 Hz. For comparison related tin(IV)
2
monoclinic space group P2
1
/n. The X-ray diffraction analysis
stannate(II) anion in two
derivatives give rise to significantly larger values for J(F,Sn)
2
119
2
119
disclosed the presence of
a
couplings ( J(F, Sn) = 353 Hz for HSn(C
451 Hz for BrSn(C ). Additionally, the signal for the CF
3
2 5 3
F ) and ( J(F, Sn) =
conformations (Figure 2). The shortest distance between a tin and
a hydrogen atom of above 340 pm is larger than the sum of the
2
F
5
)
3
3
groups at -83.0 ppm shows a clean J(F,Sn) coupling of 61 Hz
which is not resolved in the spectra of pentafluoroethyltin(IV)
compounds, and thus may be regarded as a strong evidence for
low valent tin species. The coupling to all fluorine atoms results in
[
8]
Van-der-Waals
tris(pentafluoroethyl)stannate(II) anion displays a tricoordinated
strongly pyramidalized tin atom. The electron withdrawing C
groups cause a C-Sn-C angle of 91.3° in the major conformer
radii.
As
a
consequence,
the
2
F
5
1
19
a complex septet of decets splitting pattern in the
spectrum at -163.7 ppm (Figure 3).
Sn NMR
-
comparable with the Cl-Sn-Cl angle in [SnCl
3
] (92.8°), and is
-
clearly more acute than the corresponding angle in the [SnPh
3
]
[
8,13]
ion (96.9°).
Figure 2. Molecular structure of [HBDMAN][Sn(C
groups on two positions (63:37); major conformer is shown). Thermal
ellipsoids are shown at 50 % probability. Selected bond lengths [pm] and angles
°]: Sn-C(av) 226.5, C3-Sn1-C1 91.08(10), C3-Sn1-C5 91.31(12), C1-Sn1-C5
1.51(12).
2 5 3
F ) ] (Disorder of all three
C
2
F
5
119
119
Figure 3.
Sn NMR spectrum (top) in CDCl
3
and simulated
][Sn(C ].
Sn NMR
[14]
spectrum (bottom, simulated with gNMR ) of [PPh
4
2 5 3
F )
[
9
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Our in situ generated LiSn(C
2
F
5
)
3
underwent spontaneous
assigned to the stretching vibrations of the carbonyl ligands. In
accordance to Tolman’s concept the band of the highest
reactions with benzylic and allylic halides to the corresponding
Sn(C derivatives (Scheme 3).
-
1
2
F
5
)
3
wavenumber at 2059 cm provides information on the p-acceptor
[
15]
properties of the tris(pentafluoroethyl)stannyl ligand. This band
is of slightly higher energy than those of the
tris(pentafluoroethyl)germyl, Ge(C
tris(pentafluoroethyl)silyl, Si(C , (n = 2053 cm ) ligands. The
p-acceptor properties of the tin based anion are comparable with
a
-
1
2
F
5
)
3
,
(n = 2057 cm ) and
-
1
2
5 3
F )
-
1
[12,16]
3
those of the neutral PMe ligand (n = 2064 cm ).
An unusual nucleophilic tris(pentafluoroethyl)stannate(II)
synthon represents 1,1,1-tributyl-2,2,2-tris(pentafluoroethyl)-
distannane, n-Bu
3
SnSn(C
2 5 3
F ) , which was obtained from the
reaction of HSn(C
2
5 3
F ) withtributyltin hydride. Due to the inversed
Scheme 3. Tris(pentafluoroethyl)stannylation of allyl bromide and benzyl
chloride derivatives.
polarity the product is readily formed by hydrogen elimination
(Scheme 5) and displays a highly polarized tin-tin bond in contrast
to typical distannanes. The generation of stannate anions from
distannanes usually requires the employment of strong reduction
reagents or the treatment with organolithium compounds. In our
case the addition of donor solvents effected the complete
4
-Vinylbenzyltris(pentafluoroethyl)stannane possesses a poly-
merizable functionality and thus represents a promising precursor
1
9
for polymers decorated by Lewis acidic centers. In the F NMR
3 2 5 3
dissociation of n-Bu SnSn(C F ) into a donor stabilized
2
117/119
+
-
spectrum of the monomer an increased J(F,
Sn) coupling
3 n 2 5 3
tributylstannylium cation, [n-Bu Sn(D) ] , and the [Sn(C F ) ]
constant of 294/304 Hz was observable. Tin satellites at the
anion.
2
2
resonances of the CH unit at 3.37 ppm ( J(H,Sn) = 74 Hz) in the
1
H NMR spectrum underline the identity of the product. Albeit
polymerization already occurs by mild heating we preferred the
radical polymerization induced by AIBN in toluene for the sake of
a more homogeneous product. Removal of all volatile compounds
from the molten polymer at 200 °C furnished a brittle colorless
residue which was soluble in THF but insoluble in acetonitrile.
4
Upon addition of [NBu ]I to a slurry of the polymer in acetonitrile
a clear solution was obtained indicating that the Lewis acidic tin
moiety was readily converted into a soluble iodide complex. The
Scheme 5. Synthesis and donor induced dissociation of the unsymmetrical
distannane n-Bu SnSn(C F ) .
1
9
3
2
5 3
F
NMR spectrum shows two broad signals at -82.6
1
and -112.9 ppm for the C
2 5
F groups. In the H NMR spectrum
broad resonances for the aryl protons at 7.0 and 6.4 ppm and at
An evidence for the existence of a tin-tin bond in non-polar
3
2
.1 ppm for the methylene group are observable. Resonance at
.4 and 1.5 ppm appear for the protons of the polymer backbone.
In order to investigate to p-acidity of the complexed anion
1
19
1
solvents like chloroform is provided by
spectroscopy, where the signal for the n-Bu Sn unit at 26.4 ppm
units ( J(Sn,F) = 5 Hz). In donating
Sn{ H} NMR
3
3
reveals a coupling to the CF
2
we investigated the reactivity of the isolable [PPh
towards tetracarbonylnickel. Reaction of the components in
dichloromethane quantitatively furnishes
PPh ][Ni(CO) {Sn(C }] as an off-white solid (Scheme 4).
4 2 5 3
][Sn(C F ) ]
solvents like THF, acetonitrile or DMF this additional coupling
vanished in favor of a resonance at 1.8 ppm which is attributed to
+
[17]
the donor stabilized tributylstannylium cation [n-Bu
3
Sn(D)
n
] . In
[
4
3
2 5 3
F )
1
9
-
the F NMR spectrum the resonances for the free [Sn(C
2
5 3
F ) ]
2
anion with its characteristic small J(F,Sn) coupling constant of
about 120 Hz is observable.
3 2 5 3
X-ray structural analysis of crystalline n-Bu SnSn(C F )
could be achieved by in-situ crystallization of the melt, however
the tin-tin bond length of 281.0(1) pm is not exceptional compared
Scheme 4. Formation of the tris(pentafluoroethyl)stannate(II) nickel complex.
[
18]
to other distannanes (Figure 4). The synthetical advantage of
-
2 5 3
this [Sn(C F ) ] transfer reagent is the concomitant liberation of
2
the tributylstannylium cation which may intercept halide ions
freed in substitution reactions to give tributyltin halides (Scheme
While the J(F,Sn) coupling constant of 131 Hz, characteristic for
tin(II) species, is barely influenced by complexation, the stannyl
1
19
6
). Coordination of tributylstannylium can also be used for the
ligand shows a significant up field shift to +64.9 ppm in the Sn
NMR spectrum. The existence of a nickel tin bond is also evident
[
19]
activation of carbonyl functions in alkylation reactions.
1
3
1
3 2 5 3
Additionally, the n-Bu SnSn(C F ) possesses excellent solubility
from the C{ H} NMR spectrum where the resonances of the
in nonpolar solvents like n-heptane and therefore allows a
tris(pentafluoroethyl)stannylation also in this media. If the
mechanism, however, also includes ionic intermediates in the
carbonyl ligands at 198.4 ppm are accompanied by tin satellites
2
(
J(C,Sn) = 30 Hz). The IR spectrum in dichloromethane displays
-
1
three bands at 2059 (m), 1994 (s) and 1975 (s) cm , which are
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-
absence of donors or takes another course must be proven in
following works.
Encouraged by these useful applications of the [Sn(C
2
F
5
)
3
] anion
we tried to extend the substrate spectrum to different element
chlorides such as PhSnCl , Si Cl , ClGe(C and Ph PCl.
Remarkably, the reactions with these electrophiles took a different
course. Instead of substitution products, the
dichlorotris(pentafluoroethyl)stannate(IV) anion, [SnCl (C
3
2
6
2
F
5
)
3
2
-
2
2 5 3
F ) ]
was formed, as a result of a redox process of the stannate(II)
anion (Scheme 7). We confirmed this reducing capability in
separate reactions with elemental halogens whereby a whole
-
series of dihalogenostannates, [SnX
2
(C
2
F
5
)
3
] (X = Cl, Br, I) were
obtained. These products can be independently formed by Lewis
acid base adduct formation of the halogenostannanes XSn(C F )
3 2 5 3
Scheme 6. Nucleophilic substitutions of n-Bu SnSn(C F ) with tributyltin halide
2
5 3
formation.
(
X = Cl, Br, I) with the corresponding tetraphenylphosphonium
salts. In the latter case the molecular structure could be
ascertained by an X-ray diffraction study (Figure 5). The chlorine
and bromine compound are isostructural and also the iodine
species features a distorted trigonal bipyramidal geometry with
the halide atoms in axial positions.
-
Scheme 7. [SnX
2
(C
2
F
5
)
3
] salt formation (X = Cl, Br, I).
Figure 4. Molecular structure of n-Bu
shown at 50 % probability. Selected bond lengths [pm] and angles [°]: Sn1-Sn2
81.0(1), Sn1-CF (av) 222.9, Sn2-Sn1-C(av) 117.7.
3 2 5 3
SnSn(C F ) . Thermal ellipsoids are
2
2
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Figure 5. Molecular structures of the dihalogenotris(pentafluoroethyl)stannate(IV) anions, [PPh
4
][SnX
2
(C
2
F
(C
5
)
3
] (X = Cl (left), Br (middle), I (right)). Thermal
-
-
ellipsoids are shown at 50 % probability ([SnCl
2
(C
2
F
5
)
3
] shows a disorder of two C
2
F
5
groups (75:25). [SnBr
2
2
F
5
)
3
] shows a disorder of all C
2
F
5
groups (77:23,
][SnBr (C ]:
]: Sn-I1 282.4(1), Sn-I2 285.0(1), Sn-C(av) 225.6, I1-Sn-I2 178.4(1).
6
2:38, 82:18), major conformers are shown). [PPh
4
][SnCl
2
(C
2
F
5
)
3
]: Sn-Cl1 244.2(1), Sn-Cl2 246.3(1), Sn-C(av) 222.6, Cl1-Sn-Cl2 176.3(2); [PPh
4
2
2 5 3
F )
Sn-Br1 261.4(1), Sn-Br2 258.6(1), Sn-C(av) 224.0, Br1-Sn-Br2 178.2(1); [PPh
4
][SnI
2
(C
2
F
5
)
3
3
000 ion-trap mass spectrometer (Bruker Daltonik GmbH, Bremen, Germany)
Conclusions
equipped with a standard ESI/APCI source. EI mass spectra were recorded
using an Autospec X magnetic sector mass spectrometer with EBE geometry
In conclusion we presented three different synthetic approaches
(
Vacuum Generators, Manchester, UK) equipped with a standard EI or CI
-
to the nucleophilic [Sn(C
HSn(C , (ii) direct pentafluoroethylation of tin(II) chloride as
well as (iii) solvent induced dissociation of the unsymmetrical
distannane n-Bu SnSn(C . The pentafluoroethyl groups lead
2 5 3
F ) ] anion by (i) deprotonation of
source. Melting points were measured on a Mettler Toledo Mp70 Melting Point
System. The pH value measurement were performed with a Portavo 907 Multi
2
5 3
F )
(
Knick). Vapor pressures were determined with a VAP 5 (Vacuubrand), a piezo
3
2
F
5
)
3
vacuum gauge. The crystal data were collected on a Bruker Nonius Kappa CCD
or Agilent Supernova diffractometer using graphite-monochromated Mo-
to an increased stability and allow the introduction of the
tris(pentafluoroethyl)stannyl moiety in allylic and benzylic
positions. In the latter case the appending of a styrene group
facilitated the synthesis of a Lewis acidic-decorated polymer.
Beside these nucleophilic substitutions we presented the
a
K radiation (l = 71.073 pm. The crystals were kept at 100.0(1) K during data
[
20]
collection. The structures were solved using Olex2 and refined with the ShelX
[
21]
program package using direct methods and least-squares minimization. All
atoms were refined anisotropically except for the hydrogen atoms, which were
3 2 5 3
refined isotropically. Single crystals of n-Bu SnSn(C F ) were grown by in situ
synthesis of [PPh
4 3 2 5 3
][Ni(CO) {Sn(C F ) }] and the oxidation of the
crystallization of the liquid inside a sealed capillary generating manually a crystal
seed at 234.8 K just under the melting temperature and subsequently chilling to
100 K with 50K/h. Details of the X-ray investigation are given in Table. 1. CCDC-
stannate(II) anion with elemental halogens to the corresponding
-
dihalogenotris(pentafluoroethyl)stannate(IV) salts, [Sn(C
X = Cl, Br, I), which were structurally characterized.
2 5 3 2
F ) X ]
(
2 5 3 2 5
1001351 [[HBDMAN][Sn(C F ) ]] (Disorder of all three C F groups on two
positions (63:37). The positions with the smaller occupation were restrained with
SAME to get comparable bond lengths and angles), CCDC-1549429 [n-
Bu
groups over two sites but with different occupation factors (77:23, 62:38,
2:18)), CCDC-1549431 [[PPh ][SnI (C ]], CCDC-1549432
[PPh ][SnCl (C ]] (Disorder of the group C3,C4, F6 to F10 at two
positions (75:25); refined with Ueq to be same. Disorder of the C group
3 2 5 3 4 2 2 5 3 2 5
SnSn(C F ) ], CCDC-1549430 [[PPh ][SnBr (C F ) ]] (Disorder of all C F
Experimental Section
8
4
2
2 5 3
F )
All chemicals were obtained from commercial sources and used without further
purification. Standard high-vacuum techniques were employed throughout all
[
4
2
2
F
5
)
3
2 5
C F
2
F
5
preparative procedures. Nonvolatile compounds were handled in a dry N
2
C5,C6, F11 to F15 at three positions; refined as rigid groups with Ueq to be
same.) 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.ac.uk/data_request/cif.
atmosphere using Schlenk techniques. The NMR spectra were recorded on a
1
19
Bruker Model Avance III 300 spectrometer ( H 300.13 MHz; F 282.40 MHz;
3
1
119
13
P 111.92 MHz; Sn 111.92 MHz; C 75.47 MHz) with positive shifts being
3
1
3
downfield from the external standards (85 % orthophosphoric acid ( P), CCl F
1
9
13
1
119
(
F), TMS ( C, H), SnMe
4
(
Sn)). IR spectra were recorded on an ALPHA-
Synthesis of tris(pentafluoroethyl)stannane: Bromotris(pentafluoro-
FT-IR spectrometer (Bruker). ESI mass spectra were recorded using an Esquire
2 5 3
ethyl)stannane, BrSn(C F ) , (7.49 g, 13.48 mmol) was condensed onto
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3
tributyltin hydride, n-Bu SnH, (4.02 g, 13.81 mmol) at -196 °C. The reaction
mixture was allowed to warm to -50 °C and stirred for 20 minutes. Keeping the
mixture at -25 °C, the product was condensed off into a -196 °C cooling trap in
-
6
a dynamic high vacuum (10 bar). The product was kept at temperatures below
-
(
2 5 3
60 °C to prevent decomposition. HSn(C F ) was obtained as a colorless liquid
1
5.27 g, 11.05 mmol, 82 %). Vapor pressure (22 °C)= 30mbar. H NMR
1
(
1
[D]chloroform, 298 K): d=7.75 ppm (m, J(H,Sn)=2464/2582 Hz, 1H; SnH);
3
19
2
C{ F} NMR ([D]chloroform, 298 K): d=124.4 (d,
J(C,H)=19 Hz,
1
2
19
J(C,Sn)=590/617 Hz; CF
2
), 119.0 ppm (s, J(C,Sn)=83 Hz; CF
3
); F NMR
3
(
2
[D]chloroform, 298 K): d=-83.9 (s, 9F; CF
3
), -110.5 ppm (d, J(F,H)=8 Hz,
119
1
J(F,Sn)=336/353 Hz, 6F; CF
2
); Sn{ H} NMR ([D]chloroform, 298 K): d=-
2
3
119
19
2
68.6 ppm (sept, dec, J(Sn,F)=349 Hz,
J(Sn,F)=8 Hz);
Sn{ F} NMR
1
(
[D]chloroform, 298 K): d=-268.5 ppm (d, J(Sn,H)=2588 Hz); MS (EI, 70 eV,
+
+
1
9
pos.) {m/z (%) [assignment]}: 259.0 (47) [HSnF(C
2
F
5
∙+
)] , 159.0 (22) [HSnF
2
] ,
Figure 7. F NMR spectrum of [H
3
O][Sn(C
2
F
5
)
3
] in isopropanolic NaOH solution
+
∙+
+
1
39.0 (76) [SnF] , 120.0 (13) [Sn] , 100.0 (100) [C
2
F
4
] , 69 (37) [CF
3
] ; IR (gas
at a pH value of 13.
~
-1
phase): n=1943 (w), 1322 (s), 1301 (m), 1222 (s), 940 (s), 742 (m), 528 (m) cm .
Deprotonation of tris(pentafluoroethyl)stannane with water: HSn(C
2
F
5
)
3
Synthesis
tris(pentafluoroethyl)stannate(II): Tris(pentafluoroethyl)stannane (0.55 g,
1.15 mmol) was condensed onto chilled solution (-196 °C) of
of
1-(dimethylammonium)-8-(dimethylamino)naphthalene-
was combined with D O in an NMR tube and was NMR spectroscopically
2
1
13
19
investigated. H NMR ([D
2
]water, 298 K): d=4.75 ppm (s; HOD); C{ F} NMR
a
1
([D
2
2
]water, 298 K): d=135.8 (s, J(C,Sn)=443/465 Hz; CF
2
), 121.6 ppm (s,
1,8-bis(dimethylamino)naphthalene (0.22 g, 1.03 mmol) in diethyl ether (4 mL)
and stirred for 48 h at room temperature. After removing all volatile compounds
the crude product was obtained as a yellow solid. To remove last residues of
diethyl ether the crude product was redissolved in dichloromethane. After
19
3
J(C,Sn)=22 Hz; CF
3
); F NMR ([D
2
]water, 298 K): d=-83.5 (m, J(F,Sn)=63 Hz,
2
119
1
9
2
F; CF
3
), -117.5 ppm (m, J(F,Sn)=101 Hz, 6F; CF
2
); Sn{ H} NMR ([D
2
]water,
2
3
98 K): d=-171.9 ppm (sept, dec, J(Sn,F)=106 Hz, J(Sn,F)=65 Hz) (Figure 6).
removing all volatile compounds the product was isolated as a yellow solid (0.63
1
g, 0.91 mmol, 89 %). M.p.=72-75 °C; H NMR ([D
2
4
]dichloromethane, 298 K):
3
d=19.39 (m, 1H; NH), 8.09 (d, d, J(H,H)=7.9 Hz, J(H,H)=1.5 Hz, 2H; Ar-H),
3
4
3
7
3
.82 (d, d, J(H,H)=7.8 Hz, J(H,H)=1.4 Hz, 1H; Ar-H), 7.77 (d, d, J(H,H)=7.8 Hz,
3
13
1
J(H,H)=7.8 Hz, 2H; Ar-H), 3.18 ppm (d, J(H,H)=2.8 Hz, 12H; CH
NMR ([D ]dichloromethane, 298 K): d=143.2, 135.6, 130.0, 127.3, 121.1, 118.5
2
s; arom. C), 46.3 ppm (s; CH ]dichloromethane, 298 K):
3
); C{ H}
2
1
3
19
(
3
); C{ F} NMR ([D
1
2
d=136.3 (s, J(C,Sn)=532/556 Hz; CF ), 122.3 ppm (s, J(C,Sn)=19 Hz; CF );
2
3
1
9
3
F
NMR ([D
2
]dichloromethane, 298 K): d=-83.4 (s, J(F,Sn)=62 Hz, 9F;
2
119
19
CF
[D
3
2
), -117.6 ppm (s,
J(F,Sn)=109 Hz, 6F; CF
2
);
Sn{ F} NMR
1
(
]dichloromethane,
298 K):
d=-163.7 ppm
(s,
J(Sn,C)=556 Hz,
2
119
2
J(Sn,C)=20 Hz); Sn NMR ([D ]dichloromethane, 298 K): d=-163.7 ppm (sept,
2
3
dec, J(Sn,F)=112 Hz, J(Sn,F)=65 Hz); MS (ESI, pos.) {m/z (%) [assignment]}:
+
+
2
15.1 (100) [C14
H
19
N
2
] , 200.1 (18) [C13
H
16
N
2
] ; MS (ESI, neg.) {m/z (%)
-
-
[
assignment]}: 514.6 (5) [Sn(C
2
F
5
)
3
F
2
] , 508.6 (10), 476.7 (18) [Sn(C
2
F
5
)
3
] ,
-
-
-
] ,
4
2
1
1
14.7 (12) [Sn(C
76.7 (70) [Sn(C
2
F
5
)
2
F
3
-
] , 376.7 (100) [Sn(C
2
F
5
)
2
F] , 314.7 (5) [Sn(C
2
F
5
)F
4
~
2
F
5
)F
2
] ; IR (ATR): n=1628 (w), 1604 (w), 1579 (w), 1519 (w),
477 (w), 1461 (m), 1415 (w), 1378 (w), 1297 (s), 1270 (w), 1168 (s), 1083 (s),
062 (m), 1001 (s), 921 (w), 896 (s), 831 (m), 766 (s), 723 (m), 636 (m), 588
-
1
(
m), 533 (w), 511 (w), 478 (m), 417 (w) cm .
1
19
1
Figure 6.
Sn{ H} NMR spectrum of [H O][Sn(C F ) ] in D O (top) and the
3 2 5 3 2
Synthesis of tetraphenylphosphoniumtris(pentafluoroethyl)-stannate(II):
HC (20 mmol) was condensed onto a stirred solution of n-butyllithium
11.5 mL, 18.4 mmol, 1.6 M in n-hexane) in diethyl ether (150 mL) at -80 °C.
After stirring for 20 min at -80 °C tin(II) chloride (1.05 g, 5.54 mmol) was added
and the suspension was allowed to reach room temperature overnight. [PPh ]Cl
2.74 g, 7.31 mmol) was added to the crude product suspension and stirred for
[14]
simulated spectrum (bottom, simulated with gNMR ).
2
F
5
(
2 5 3
Due to fast decomposition of HSn(C F ) in neutral and basic aqueous media
4
the following titration experiments were carried out in isopropanol with 0.5 %
water by adding a 0.006 M isopropanolic NaOH solution to an isopropanolic
(
4
8 h. The precipitate was filtered off and the solvent was removed under
2 5 3 a
solution of HSn(C F ) . It was assumed that the pK value of 0.8 in this medium
reduced pressure. After recrystallization in chloroform/n-pentane the product
corresponds to the half equivalence point (4.0 mL/0.8) and that the equivalence
point matches the point of the maximum gradient ∂pH/∂V. In aqueous media the
equivalence point for strong acid also matches the neutral point. In our
experiments in isopropanol these two characteristic points do not coincide.
However, a determination of the half equivalence point (4.2 mL/0.8) relative to
was obtained as an off-white solid (3.53 g, 4.33 mmol, 78 %). M.p.
1
(
(
decomp.)=102 °C; H NMR ([D]chloroform, 298 K): d=7.90 (m, 4H; Ar-H), 7.76
1
3
1
m, 8H; Ar-H), 7.61 ppm (m, 8H; Ar-H); C{ H} NMR ([D]chloroform, 298 K):
4
2
d=135.8 (d, J(C,P)=3 Hz; para-C), 134.3 (d, J(C,P)=10 Hz; ortho-C), 130.7 (d,
3
1
13
19
J(C,P)=13 Hz; meta-C), 117.4 ppm (d, J(C,P)=90 Hz; ipso-C); C{ F} NMR
1
a
the neutral point at 8.3 mL/7.0 led to the same pK -value of 0.8. In order to
(
2
[D]chloroform, 298 K): d=135.9 (s, J(C,Sn)=526/548 Hz; CF
2
), 122.3 ppm (s,
confirm that no decomposition occurs during the measurements the solution
was NMR spectroscopically investigated at a pH value of 13 in a separated run
19
J(C,Sn)=19 Hz; CF
3
);
F
NMR ([D]chloroform, 298 K): d=-83.0 (m,
3
2
31
1
J(F,Sn)=61 Hz, 9F; CF
3
2
), -117.5 ppm (m, J(F,Sn)=117 Hz, 6F; CF ); P{ H}
1
3
2 5
to find traces of HC F (Figure 7).
NMR ([D]chloroform, 298 K): d=23.3 (s, J(C,P)=90 Hz, J(C,P)=13 Hz,
2
119
19
J(C,P)=10 Hz);
Sn{ F} NMR ([D]chloroform, 298 K): d=-163.7 ppm (s);
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201702855
FULL PAPER
1
19
1
2
Sn{ H} NMR ([D]chloroform, 298 K): d=-163.7 ppm (sept, dec, J(Sn,F)=119
(200 °C). In a standard distillation apparatus thermally induced polymerization
is predominant. The product was obtained as a colorless liquid (3.94 g,
3
Hz, J(Sn,F)=63 Hz).
1
3
6
.65 mmol, 68 %). H NMR ([D]chloroform, 298 K): d=7.39 (d, J(H,H)=8.3 Hz,
3
3
2
H; Ar-H), 7.20 (d, J(H,H)=8.3 Hz, 2H; Ar-H), 6.72 (d, d, J(H,H)=17.6 Hz,
2 5
Synthesis of allyltris(pentafluoroethyl)stannane: HC F (50 mmol) was
3
7
3
J(H,H)=10.9 Hz, J(H,Sn)= 5.7 Hz, 1H; CH), 5.78 (d, J(H,H)=17.6 Hz,
condensed onto a stirred solution of n-butyllithium (29 mL, 46 mmol, 1.6 M in n-
hexane) in diethyl ether (300 mL) at -80 °C. After stirring for 20 min at -80 °C
tin(II) chloride (2.56 g, 13.50 mmol) was added and the suspension was stirred
for 3 h until it reached -20 °C. The two-phase system was concentrated at
reduced pressure until the clear upper phase had vanished. Allyl bromide
8
3
8
J(H,Sn)=7.3 Hz, 1H; =CH
2
(cis)), 5.30 (d, J(H,H)=10.8 Hz, J(H,Sn)=7.7 Hz,
2
13
1
1
H; =CH (trans)), 3.37 ppm (s, J(H,Sn)=74 Hz, 2H; CH ); C{ H} NMR
2
2
5
([D]chloroform, 298 K): d=136.5 (s, J(C,Sn)=28 Hz; para-C), 136.0 (s,
6
2
J(C,Sn)=16 Hz; =CH), 131.6 (s, J(C,Sn)=60/63 Hz; ipso-C), 128.4 (s,
J(C,Sn)=39 Hz; arom. C), 127.0 (s, J(C,Sn)=23 Hz; arom. C), 114.0 (s,
(
2.23 g, 18.43 mmol) was condensed onto the residue (-196 °C) and the
7
1
13
19
J(C,Sn)=13 Hz; =CH
2
), 22.0 ppm (s, J(C,Sn)=339/356 Hz; CH
2
); C{ F} NMR
), 119.3 ppm (s,
),
suspension was stirred overnight at ambient temperature. After fractional
condensation into a -40 °C cooling trap the crude product was purified via
1
(
2
[D]chloroform, 298 K): d=125.7 (s, J(C,Sn)=441/461 Hz; CF
2
19
J(C,Sn)=75/79 Hz; CF
3
); F NMR ([D]chloroform, 298 K): d=-82.9 (s, 9F; CF
3
distillation (52 °C at 20 mbar). The product was obtained as a colorless liquid
2
119
19
1
2
-110.6 ppm (s, 6F, J(F,Sn)=294/304 Hz; CF ); Sn{ F} NMR ([D]chloroform,
(
3.04 g, 5.88 mmol, 44 %). H NMR ([D]chloroform, 298 K): d=5.90 (m, 1H;
2
119
3
3
2
2
98 K): d=-200.6 ppm (t, m, J(Sn,H)=76 Hz);
Sn NMR ([D]chloroform,
=
CH), 5.30 (d, J(H,H)=16.9 Hz, 1H; =CH
2
(cis)), 5.18 (d, J(H,H)=10.1 Hz, 1H;
2
2
3
2
98 K): d=-200.6 ppm (sept, t, J(Sn,F)=306 Hz, J(Sn,H)=76 Hz).
=
1
CH
2
1
(trans)), 2.77 ppm (d, J(H,H)=8.3 Hz, J(H,Sn)=81.2 Hz, 2H; CH
2
);
3
C{ H} NMR ([D]chloroform, 298 K): d=127.5 (s, J(C,Sn)=73 Hz; =C), 118.9 (s,
1
13
19
J(C,Sn)=80 Hz; =C), 19.7 ppm (s, J(C,Sn)=344/360 Hz; CH
2
); C{ F} NMR
Polymerization of 4-vinylbenzyltris(pentafluoroethyl)stannane: A sample
of 4-vinylbenzyltris(pentafluoroethyl)stannane (2.01 g, 3.39 mmol) was
dissolved in toluene (12 mL) and azoisobutyronitrile (16 mg, 0.10 mmol) was
added. The solution was degassed (3 x freeze-pump-thaw cycles) and stirred
for 48 h at 75 °C. All highly volatile compounds were removed under reduced
pressure which yielded in an oily residue. To remove low-volatile impurities the
residue was heated up to 200 °C in high vacuum. After cooling to room
temperature a brittle solid (1.01 g) was obtained. The product was suspended
1
(
2
[D]chloroform, 298 K): d=125.5 (s, J(C,Sn)=451/471 Hz; CF ), 119.3 ppm (s,
2
19
J(C,Sn)=76/80 Hz; CF
3
); F NMR ([D]chloroform, 298 K): d=-83.5 (s, 9F; CF
3
),
2
119
1
-
111.2 ppm (s, J(F,Sn)=296 Hz, 6F; CF
2
);
Sn{ H} NMR ([D]chloroform,
2
119
19
2
98 K): d=-191.0 ppm (sept, J(Sn,F)=302 Hz); Sn{ F} NMR ([D]chloroform,
2
3
2
4
98 K): d=-191.4 ppm (t, d, d, d, J(Sn,H)=82 Hz, J(Sn,H)=33 Hz,
4
J(Sn,H)=33 Hz, J(Sn,H)=39 Hz). MS (EI, 70 eV, pos.) {m/z (%) [assignment]}:
∙
+
+
5
17.9 (<1) [C
3
H
5
Sn(C
2
F
5
)
3
] , 398.9 (1) [C
3
H
5
Sn(C
2
F
5
)
2
] , 299.0 (1)
+
+
∙+
[
[
C
3
3
H
H
5
5
Sn(C
2
F
5
)F] , 199.0 (1) [C
3
H
5
SnF
2
] , 180.0 (1) [C
3
H
5
SnF] , 160.1 (27)
in acetonitrile and 0.5 equivalents [NBu
NMR spectroscopically investigated.
d=7.00 (m, broad, 2H; Ar-H), 6.43 (m, broad, 2H; Ar-H), 3.32 (m, broad, 2H;
CH -Sn), 3.13 (m, 8H; NBu ), 2.40 (s, broad, 1H, CH) 1.64 (m, 8H; NBu ), 1.5
), 1.00 ppm
]acetonitrile, 298 K): d=-82.6 (s,
).
4
]I were added. The formed solution was
∙
+
+
+
+
1
C
C
2
~
F
5
] , 138.9 (8) [SnF] , 91.1 (29) [C
3
H
5
CF
2
] , 41.1 (100) [C
3
H
5
] ; IR
3
H NMR ([D ]acetonitrile, 298 K):
(
ATR): n=1634 (w), 1426 (w), 1314 (s), 1294 (m), 1192 (s), 1086 (s), 987 (w),
-
1
9
29 (s), 755 (w) 737 (s), 675 (w), 603 (w), 536 (w), 495 (w) cm .
2
4
4
3
3
(
(
2 4
s, broad; CH ), 1.38 (q, t, J(H,H)=7.3 Hz, J(H,H)=7.3 Hz, 8H; NBu
3
19
t, J(H,H)=7.3 Hz, 12H; NBu
4
); F NMR ([D
3
2 5
Snythesis of benzyltris(pentafluoroethyl)stannane: HC F (11 mmol) was
broad, 9F; CF
3
), -112.9 ppm (s, broad, 6F; CF
2
condensed onto a stirred solution of n-butyllithium (4.25 g, 10 mmol, 1.6 M in n-
hexane) in diethyl ether (50 mL) at -80 °C. After stirring for 20 min at -80 °C
tin(II) chloride (0.55 g, 2.90 mmol) was added and the suspension was allowed
to reach room temperature overnight. The crude product solution was cooled
down to -50 °C and benzyl chloride (0.43 g, 3.40 mmol) was added. The
suspension was stirred for 12 h at room temperature. After removal of all highly
volatile compounds the product was distilled out of the oily residue in high
Synthesis
of
tetraphenylphosphoniumtricarbonyl[tris(pentafluoro-
][Sn(C ] (0.48 g, 0.59 mmol)
ethyl)stannyl]nickelate: A sample of [PPh
4
2 5 3
F )
was dissolved in chloroform (10 mL) and tetracarbonylnickel (0.12 g,
0.70 mmol) was condensed onto the solution. The solution was allowed to warm
to room temperature accompanied with CO generation. After stirring for 4 h all
volatile compounds were removed in vacuum. The product was obtained as a
vacuum. The product was obtained as a colorless liquid (1.23 g, 2.17 mmol,
1
1
7
2
5 %). H NMR ([D]chloroform, 298 K): d=7.40-7.20 (m, 5H; Ar-H), 3.39 ppm (s,
colorless solid (0.57 g, 0.60 mmol, 101 %). M.p.=59 °C; H NMR ([D]chloroform,
13
1
J(H,Sn)=72/75 Hz, 2H; CH
2
); C{ H} NMR ([D]chloroform, 298 K): d=132.2 (s;
298 K): d=7.94 (m, 4H; Ar-H), 7.79 (m, 8H; Ar-H), 7.64 ppm (m, 8H; Ar-H);
1
3
1
2
ipso-C), 129.2 (s, J(C,Sn)=21 Hz; arom. C), 128.1 (s, J(C,Sn)=38 Hz; arom. C),
C{ H} NMR ([D]chloroform, 298 K): d=198.4 (s, J(C,Sn)=30 Hz; CO), 135.8
1
4
2
1
1
26.9 (s, J(C,Sn)=25 Hz; arom. C), 22.1 ppm (s, J(C,Sn)=344/360 Hz; CH
2
2
);
),
(d, J(C,P)=3 Hz; para-C), 134.3 (d, J(C,P)=10 Hz; ortho-C), 130.7 (d,
3
3
19
1
1
13
19
C{ F} NMR ([D]chloroform, 298 K): d=125.7 (s, J(C,Sn)=445/465 Hz; CF
J(C,P)=13 Hz; meta-C), 117.4 ppm (d, J(C,P)=90 Hz; ipso-C); C{ F} NMR
2
19
1
1
8
19.4 ppm (s, J(C,Sn)=75/79 Hz; CF
3
); F NMR ([D]chloroform, 298 K): d=-
([D]chloroform, 298 K): d=130.6 (s, J(C,Sn)=213/222 Hz; CF
2
2
), 121.5 ppm (s,
2
119
1
19
3.2 (s, 9F; CF
3
), -110.8 ppm (s, J(F,Sn)=293/305 Hz, 6F; CF
2
); Sn{ H} NMR
J(C,Sn)=42 Hz; CF
3
);
F NMR ([D]chloroform, 298 K): d=-82.5 (s,
2
119
19
3
2
31
1
(
[D]chloroform, 298 K): d=-199.8 ppm (sept, J(Sn,F)=305 Hz); Sn{ F} NMR
J(F,Sn)=26 Hz, 9F; CF
3
), -117.5 ppm (s, J(F,Sn)=131 Hz, 6F; CF
2
); P{ H}
2
119
(
[D]chloroform, 298 K): d=-199.8 ppm (t, m, J(Sn,H)=76 Hz). MS (EI, 70 eV,
NMR ([D]chloroform, 298 K): d=23.4 ppm (s);
Sn NMR ([D]chloroform,
∙
+
2
3
pos.) {m/z (%) [assignment]}: 568.0 (1) [PhCH
2
Sn(C
2
F
5
)
3
] , 449.0 (1)
298 K): d=64.9 ppm (sept, dec, J(Sn,F)=131 Hz, J(Sn,F)=27 Hz). MS (ESI,
+
+
+
+
[
[
PhCH
2
Sn(C
2
F
5
)
2
] , 211.0 (1) [PhCH
2
Sn] , 91.1 (100) [PhCH
2
] , 65.1 (10)
pos.) {m/z (%) [assignment]}: 339.2 (100) [PPh
4
] ; MS (ESI, neg.) {m/z (%)
+
~
-
C
5
H
5
] . IR (ATR): n=3069 (w), 3035 (w), 1602 (w), 1495 (w), 1455 (w), 1408
[assignment]}: 984.4 (4), 590.5 (21) [Ni(CO)
2
{Sn(C
2 5 3
F ) }] , 562.6 (72)
-
-
-
(
w), 1313 (s), 1293 (m), 1192 (s), 1086 (s), 1031 (w), 929 (s), 810 (w), 757 (w),
[Ni(CO){Sn(C
(5) [Sn(C
2
F
5
-
)
3
}] , 534.7 (45) [Ni{Sn(C
2
F
5
)
3
}] , 476.8 (100) [Sn(C F ) ] , 377.0
2 5 3
-
1
~
7
37 (m), 696 (m), 603 (s), 586 (w), 535 (w), 446 (w) cm .
2
F
5
)
2
F] , 218.8 (9), 176.8 (21). IR (ATR): n=3065 (w), 2962 (w), 2060
(
m), 1994 (s), 1975 (s), 1588 (w), 1486 (w), 1439 (w), 1300 (m), 1174 (s), 1106
m), 1091 (s), 1078 (m), 1026 (m), 998 (w), 905 (m), 803 (w), 721 (s), 687 (s),
(
Synthesis
of
36 mmol) was condensed onto a chilled solution (-80 °C) of n-butyllithium
13.48 g, 31.72 mmol, 1.6 M in n-hexane) in diethyl ether (50 mL). After stirring
4-vinylbenzyltris(pentafluoroethyl)stannane:
2 5
HC F
-
1
5
93 (w), 525 (s), 487 (w), 462 (m), 428 (w) cm .
(
(
for 20 min at -80 °C tin(II) chloride (1.89 g, 9.97 mmol) was added and the
suspension was allowed to warm to room temperature within h. The
suspension was cooled down again (-40 °C) and 4-vinylbenzyl chloride (1.50 g,
.83 mmol) was added. After stirring at room temperature overnight the
Synthesis
Tributyltin hydride (0.33 g, 1.13 mmol) was combined in a Young valve ampoule
with n-pentane (4 mL) and HSn(C (0.62 g, 1.30 mmol) by condensation.
After stirring for 12 h at ambient temperature the solvent and all volatile
compounds were removed in high vacuum to obtain n-Bu SnSn(C as a
colorless oil (0.85 g, 1.11 mmol, 98 %). H NMR ([D]chloroform, 298 K): d=1.60-
of
1,1,1-tributyl-2,2,2-tris(pentafluoroethyl)distannane:
2
2
5 3
F )
9
suspension was filtrated and the solvent was removed at reduced pressure
yielding a brown oily residue. The product was condensed (-196 °C) into a
separate flask through a short glass tube while fast heating of the oily residue
3
2 5 3
F )
1
3
13
1
2 3
1.30 (m, 18H; CH ), 0.94 ppm (t, J(H,H)=7.3 Hz, 9H; CH ); C{ H} NMR
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201702855
FULL PAPER
2
1
(
[D]chloroform, 298 K): d=29.6 (s, J(C,Sn)=19/24 Hz; CH
2
), 27.0 (s,
(decomp.)=131-133 °C; H NMR (dichloromethane/[D
6
]acetone, 298 K): d=7.93
3
4
1
3
3
J(C,Sn)=66/69 Hz, J(C,Sn)=6 Hz; CH
2
13
), 13.2 (s, J(C,Sn)=286/299 Hz,
(d, J(H,H)=8.0 Hz, 2H; Ar-H), 7.70 (d, J(H,H)=7.6 Hz, 2H; Ar-H), 7.60 (m, 2H;
2
19
13
1
J(C,Sn)=61 Hz; CH
2
), 13.2 ppm (s; CH
3
2
); C{ F} NMR ([D]chloroform, 298 K):
Ar-H),
(dichloromethane/[D
118.3 (s; arom.
(dichloromethane/[D
113.4 ppm (s,
(dichloromethane/[D
3.06 ppm
(m,
broad,
12H;
CH
3
);
);
);
C{ H}
NMR
1
d=126.0 (s, J(C,Sn)=144/151 Hz, J(C,Sn)=4 Hz; CF
2
), 119.9 ppm (s,
6
]acetone, 298 K): d=143.0, 135.5, 129.8, 127.1, 121.1,
2
19
13
19
J(C,Sn)=60/63 Hz; CF
J(F,Sn)=13 Hz, 9F; CF
3
);
F
NMR ([D]chloroform, 298 K): d=-82.9 (s,
C),
46.5 ppm
(s,
CH
3
C{ F}
NMR
),
NMR
), -111.7 ppm (s,
Sn NMR (dichloromethane/[D ]acetone,
298 K): d=-447.2 ppm (sept, J(Sn,F)=479 Hz); MS (ESI, pos.) {m/z (%)
3
2
119
1
2
3
), -111.0 ppm (s, J(F,Sn)=237 Hz, 6F; CF
2
); Sn{ H}
6
]acetone, 298 K): d=120.2 (s; J(C,Sn)=123/130 Hz; CF
3
3
1
1
19
NMR ([D]chloroform, 298 K): d=26.4 (sept, J(Sn,F)=5 Hz, J(Sn,Sn)=865 Hz,
J(C,Sn)=846/887 Hz;
CF
2
F
1
2
J(Sn,C)=300 Hz; n-Bu
J(Sn,F)=14 Hz; Sn(C
3
Sn), -224.1 ppm (sept, dec, J(Sn,F)=241 Hz,
6
]acetone, 298 K): d=-78.2 (s, 9F; CF
3
3
119
19
2
119
2
F
5
)
3
);
Sn{ F} NMR ([D]chloroform, 298 K):
]DMF
]dimethylformamide,
), 1.41-1.31 (m, 12H; CH ), 0.91 ppm (t,
]dimethylformamide, 298 K):
J(F,Sn)=458/477 Hz, 6F; CF
2
);
2
6
d=-224.1 ppm (sept, J(Sn,H)=31 Hz). The product was dissolved in [D
7
1
+
+
and NMR spectroscopically investigated. H NMR ([D
7
[assignment]}: 557.1 (13) [(C14
H
19
N
2
)
2
I] , 215.1 (100) [C14
H
19
N
2
-
] ; MS (ESI,
2
3
98 K): d=1.64 ppm (m, 6H; CH
2
1
2
neg.) {m/z (%) [assignment]}: 986.5 (7) [SnI
2
(C (HI)
2
F
5
)
3
2
] , 886.8 (7)
13
-
-
-
J(H,H)=7.3 Hz, 9H; CH
3
), C{ H} NMR ([D
7
[SnI
2
(C
2
F
5
)
2
F(HI)
2
] , 858.7 (17) [SnI
2
(C
2
F
5
)
3
(HI)] , 730.4 (15) [SnI
2
(C
2 5 3
F ) ] ,
2
3
-
-
~
d=22.6 ppm (s, J(C,Sn)=28 Hz; CH
1
2
), 21.4 (s, J(C,Sn)=74 Hz; CH
2
), 13.3 (s,
620.5 (14) [SnI(C
2
F
5
)
3
(OH)] , 516.7 (30), 476.9 (100) [Sn(C
2
F
5
)
3
] . IR (ATR): n
13
19
J(C,Sn)=444/463 Hz;
[D ]dimethylformamide, 298 K): d=130.7 (s, J(C,Sn)=530/555 Hz; CF
17.4 ppm (s, J(C,Sn)=18 Hz; CF
CH
2
),
7.9 ppm
(s;
CH
3
);
C{ F}
NMR
),
7
]dimethylformamide, 298 K):
=1461 (w), 1299 (s), 1273 (m), 1184 (s), 1080 (s), 1022 (m), 1001 (m), 908 (s),
1
-1
(
7
2
831 (m), 755 (m), 732 (m), 608 (m), 587 (m), 533 (w), 473 (w), 428 (w) cm .
2
19
1
3
); F NMR ([D
), -122.7 ppm (s, J(F,Sn)=123 Hz; CF
]dimethylformamide, 298 K): d=1.8 ppm (s; n-Bu Sn);
]dimethylformamide, 298 K): d=-166.0 ppm (s; Sn(C );
Sn)
3
2
d=-88.5 (s, J(F,Sn)=63 Hz; CF
1
3
2
);
Synthesis
of
1-(dimethylammonium)-8-(dimethylamino)naphthalene-
19
1
Sn{ H} NMR ([D
7
3
dibromotris(pentafluoroethyl)stannate(IV): Following the previous protocol
tris(pentafluoroethyl)stannane (0.50 g, 1.05 mmol) was reacted with 1,8-
bis(dimethylamino)naphthalene (0.21 mg, 0.98 mmol) and bromine (0.19 g,
1
19
19
Sn{ F} NMR ([D
7
2 5 3
F )
+
MS (ESI, acetonitrile, pos.) {m/z (%) [assignment]}: 599.0 (100) [(n-Bu
3
2
F] ,
] , 122.7
3
4) [SnH ] ; MS (ESI, acetonitrile, neg.) {m/z (%) [assignment]}: 998.1 (17),
+
+
+
2
3 2 2
91.0 (24) [n-Bu Sn] , 234.9 (19) [n-Bu SnH] , 178.8 (14) [n-BuSnH
1
.19 mmol) was added in diethyl ether (4 mL). Removing all volatile compounds
furnished the product as reddish solid (0.85 g, 1.00 mmol, 102 %).
NMR (chloroform/[D ]acetone, 298 K):; d=7.88 (d,
J(H,H)=8.3 Hz, 2H; Ar-H), 7.70 (d, J(H,H)=7.6 Hz, 2H; Ar-H), 7.57 (m, 2H; Ar-
+
(
a
-
1
9
80.2 (42), 898.3 (26), 884.3 (92) [n-Bu
3
SnSn(C
2
F
5
)
4
-
] , 784.4 (20) [n-
M.p.=86 °C;
3
H
6
-
3
Bu
3
SnSn(C
2
F
5
)
3
F] , 606.5 (17), 514.5 (100) [Sn(C
2
F
5
)
3
F
2
] , 506.5 (69), 414.6
-
~
(
35) [Sn(C
2
F
5
)
2
F
3
] ; IR (ATR): n = 2963 (w), 2927 (w), 2877 (w), 2859 (w), 1465
13
19
H), 3.07 ppm (m, broad, 12H; CH
3
); C{ F} NMR (chloroform/[D
J(C,Sn)=984/1030 Hz; CF ), 120.2 ppm (s,
3 6
); F NMR (chloroform /[D ]acetone, 298 K): d=-79.6
6
]acetone,
1
(
w), 1421 (w), 1381 (w), 1309 (s), 1280 (m), 1189 (s), 1110 (s), 1098 (s), 1076
s), 1027 (w), 1002 (w), 961 (w), 922 (s), 878 (w), 770 (w), 735 (m), 696 (w),
2
98 K): d=121.1 (s,
2
2
19
(
J(C,Sn)=125/131 Hz; CF
s, 9F; CF ), -112.1 ppm (s, J(F,Sn)=470/492Hz, 6F; CF
chloroform/[D
-
1
6
00 (w), 534 (w), 507 (w), 451 (w), 429 (w) cm .
2
119
(
(
3
2
);
Sn NMR
2
6
]acetone, 298 K): d=-379.9 ppm (sept, m, J(Sn,F)=495 Hz); MS
+
Reaction of 1,1,1-tributyl-2,2,2-tris(pentafluoroethyl)distannane with
iodomethane: In an NMR tube n-Bu SnSn(C was combined with diethyl
ether and an excess of iodomethane. The solution was NMR spectroscopically
(ESI, pos.) {m/z (%) [assignment]}: 511.2 (8) [(C14
H
19
N
2
)
2
Br] , 295.1 (5)
+
+
3
2
F
5
)
3
[(C14H N )(HBr)] , 215.1 (100) [C14H N ] ; MS (ESI, neg.) {m/z (%)
19 2 19 2
-
-
2 2 5 3 2 5 3
[assignment]}: 634.5 (62) [SnBr (C F ) ] , 572.7 (100) [SnBr(C F ) OH] , 116.7
1
-
~
investigated and revealed the signals for MeSn(C
2
F
5
)
3
and n-Bu
]acetone, 298 K): d=2.3-1.8 (m, 18H; CH ), 1.45 ppm (t, 9H,
]acetone, 298 K): d=29.5
), 26.9 (s, J(C,Sn)=62/65 Hz; CH ), 16.1 (s,
), -8.3 ppm (s, J(C,Sn)=398 Hz,
C{ F} NMR (diethyl ether/[D ]acetone, 298 K): d=125.4 (q,
3
SnI. H NMR
(35) [BrF(OH)] . IR (ATR): n=2961 (w), 2924 (w), 2853 (w), 1477 (w), 1462 (w),
(
3
diethyl ether/[D
6
2
1302 (m), 1260 (m), 1184 (s), 1085 (s), 1028 (m), 915 (s), 830 (m), 797 (m), 766
13
1
-1
J(H,H)=7.3 Hz; CH
3
); C{ H} NMR (diethyl ether/[D
6
(s), 734 (m), 608 (m), 585 (m), 539 (w), 510 (w), 464 (m) cm .
2
3
(
1
s, J(C,Sn)=23 Hz; CH
2
2
1
2 3
J(C,Sn)=305/320 Hz; CH ), 13.3 (s; CH
Synthesis
of
1-(dimethylammonium)-8-(dimethylamino)naphthalene-
1
3
19
MeSn);
3
6
dichlorotris(pentafluoroethyl)stannate(IV): Following the previous protocol
tris(pentafluoroethyl)stannane (0.61 g, 1.28 mmol) was reacted with 1,8-
bis(dimethylamino)naphthalene (0.21 mg, 0.98 mmol) in diethyl ether (4 mL).
The residue was redissolved in dichloromethane (4 mL) and reacted with
gaseous chlorine (1.2 mmol). Removing all volatile compounds furnished the
1
2
J(C,H)=1 Hz, J(C,Sn)=515/539 Hz; CF
2
), 120.0 ppm (s, J(C,Sn)=76/80 Hz;
1
9
CF
CF
3
3
);
), -113.5 ppm (s, J(F,Sn)=303/315 Hz, 6F; CF
]acetone, 298 K): d=75.2 (s; n-Bu SnI), -148.3 ppm (sept,
Sn{ F} NMR (diethyl ether/[D ]acetone,
SnI), -148.3 ppm (q, J(Sn,H)=69 Hz; MeSn(C ).
F
NMR (diethyl ether/[D ]acetone, 298 K): d=-83.5 (s, 9F;
6
2
119
1
2
);
Sn{ H} NMR (diethyl
ether/[D
2
6
3
119
19
J(Sn,F)=315 Hz, MeSn(C
98 K) d=75.2 (m; n-Bu
2
F
5
)
3
);
6
product without further purification as a colorless solid (0.75 g, 0.98 mmol,
2
2
3
2
F
5
)
3
1
1
00 %). M.p.=85-90 °C;
6
H NMR (dichloromethane/[D ]acetone, 298 K):
3
3
d=19.14 (s, 1H; NH), 7.93 (d, J(H,H)=8.1 Hz, 2H; Ar-H), 7.70 (d, J(H,H)=7.6
1
3
1
Reaction of 1,1,1-tributyl-2,2,2-tris(pentafluoroethyl)distannane with allyl
bromide: In an NMR tube n-Bu SnSn(C was combined with n-heptane and
an excess of allyl bromide. After 72 h the solution was NMR spectroscopically
Hz, 2H; Ar-H), 7.60 (m, 2H; Ar-H), 3.06 ppm (m, broad, 12H; CH
(dichloromethane/[D ]acetone, 298 K): d=143.3, 135.4, 129.7, 127.1, 121.1,
118.3 (s; arom.
(dichloromethane/[D
CF ), 120.2 ppm
(dichloromethane/[D
3
); C{ H} NMR
3
2
F
5
)
3
6
1
3
19
C{ F}
C),
46.1 ppm
(s,
CH
3
);
NMR
1
investigated and revealed the signals for (H
5
C
3
)Sn(C
2
F
5
)
3
and n-Bu
SnBr), -
Sn{ F} NMR (n-
SnBr), -191.4 ppm (t, d, d, d,
3
SnBr.
6
6
]acetone, 298 K): d=124.0 (s, J(C,Sn)=1051/1100 Hz;
1
19
1
2
19
Sn{ H} NMR (n-heptane/[D
6
]acetone, 298 K): d=125.5 (s; n-Bu
3
2
(s,
J(C,Sn)=123/128 Hz;
CF
3
);
), -114.1 ppm (s,
Sn NMR (dichloromethane/[D ]acetone,
298 K): d=-364.0 ppm (sept, J(Sn,F)=490 Hz). MS (ESI, pos.) {m/z (%)
F
NMR
2
119
19
1
91.4 ppm (sept, J(Sn,F)=301 Hz, (H
5
C
3
)Sn(C
2
F
5
)
3
);
]acetone, 298 K): d=-81.0 (s, 9F; CF
3
2
119
heptane/[D
2
6
]acetone, 298 K): d=125.8 (m; n-Bu
3
J(F,Sn)=465/486Hz, 6F; CF
2
2
);
6
3
4
4
J(Sn,H)=82 Hz, J(Sn,H)=33 Hz, J(Sn,H)=33 Hz, J(Sn,H)=39 Hz).
+
[
19 2
assignment]}: 215.1 (100) [C14H N ] ; MS (ESI, neg.) {m/z (%) [assignment]}:
-
~
5
1
9
5
2 2 5 3
46.7 (100) [SnCl (C F ) ] ; IR (ATR): n=3057 (w), 2952 (w), 1512 (w), 1477 (w),
Synthesis
diiodotris(pentafluoroethyl)stannate: HSn(C
condensed onto solution of 1,8-bis(dimethylamino)naphthalene (0.42 g,
.96 mmol) in dichloromethane (4 mL). After stirring for 20 min all volatile
of
1-(dimethylammonium)-8-(dimethylamino)naphthalene-
467 (w), 1415 (w), 1306 (m), 1207 (s), 1183 (s), 1091 (s), 1030 (w), 1003 (w),
51 (w), 921 (s), 831 (w), 767 (m), 734 (m), 692 (m), 607 (m), 588 (m), 547 (m),
2
5 3
F )
(1.29 g, 2.71 mmol) was
a
-
1
34 (m), 512 (m), 476 (m), 410 (m) cm .
1
compounds were removed under reduced pressure. The residue was
redissolved in dichloromethane (4 mL) and iodine (0.54 g, 2.13 mmol) was
sublimated onto the solution. After 1 h at room temperature all volatile
compounds were removed and residue was recrystallized from chloroform to
-
Synthesis of the tetraphenylphosphonium salts of [Sn(C
2
F
5
)
3
Cl
]Cl were reacted with a
slight excess of the corresponding halido-tris(pentafluoroethyl)stannane,
XSn(C (X = Cl, Br, I), in dichloromethane (5 mL). Removal of all volatile
2
] ,
-
-
2 5 3 2 2 5 3 2 4 4 4
[Sn(C F ) Br ] , [Sn(C F ) I ] : [PPh ]I, [PPh ]Br, [PPh
obtain the product as
a
yellowish solid (1.48 g, 1.57 mmol, 80 %). M.p.
2 5 3
F )
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201702855
FULL PAPER
compounds after 1 h in high vacuum furnished the tetraphenylphosphonium
salts in yields of 90-96 %. Crystals suitable for X-ray diffraction were obtained
by cooling (-25 °C) a dichloromethane or chloroform solution.
Table 1. Structure refinement data of [HBDMAN][Sn(C
HBDMAN][Sn(C
2
F
5
)
3
], n-Bu
3
SnSn(C
2
F
5
)
3
, [PPh
4
][SnBr
] [SnBr
CHCl
2
(C
2
F
5
)
3
], [PPh
4
][SnI
2
(C
2
F
5
)
3
], [PPh
4
][SnCl
2
(C
2
F
5
)
3
].
[
PPh
4
2
(C
2
F
5
)
3
]
[PPh ] [SnI (C F ) ]
[PPh ][SnCl (C F ) ]
4
2
2
5
3
4
2
2
5 3
[
2
F
5
)
3
]
n-Bu SnSn(C F )
3
2 5 3
∙
3
∙CH
2
Cl
2
∙CHCl
3
Crystallographic Section
empirical formula
a / pm
b / pm
c / pm
C
20
H
19
F
15
N
2
Sn
C
18
H
27
F
15Sn
2
C
31
H
21Br
2
Cl
3
F
15PSn
C
31
H
22Cl
2
F
15
I
2
PSn
31 5
C H21Cl F15PSn
973.860(10)
1391.95(2)
1879.01(3)
90
924.151(14)
965.64(2)
1762.32(3)
75.9844(18)
78.8093(14)
62.441(2)
1346.57(5)
2
909.049(7)
1884.257(15)
2196.822(17)
90
1256.68(2)
1288.41(2)
1317.12(2)
904.198(8)
1870.993(17)
2181.33(2)
90
a / °
77.0025(16)
64.7893(18)
78.9033(17)
1868.67(7)
2
b / °
100.6901(8)
90
90.0305(7)
90
91.7467(8)
90
g / °
6
3
V / 10 pm
2505.91(6)
4
3762.90(5)
4
3688.55(6)
4
Z
-
3
ρ
calc / mg∙mm
1.834
1.889
1.932
2.051
1.810
crystal system
space group
monoclinic
triclinic
monoclinic
triclinic
monoclinic
P2
1
/c
P-1
P2
1
/c
P-1
1
P2 /c
shape / color
colorless fragment
0.30 x 0.28 x 0.27
colorless in a capillary
0.30 × 0.15 × 0.14
colorless fragment
0.24 × 0.20 × 0.10
colorless fragment
0.31 × 0.24 × 0.19
colorless fragment
0.32 × 0.25 × 0.12
-
3
crystal size / mm
Data Collection
diffractometer
Nonius Kappa CCD
Agilent Supernova
1.963
Agilent Supernova
3.157
Agilent Supernova
2.620
Agilent Supernova
1.199
1
μ / mm
-
1.145
100(2)
1352
T / K
100.0(1)
100.0(1)
100.0(1)
100.0(1)
F(000)
740.0
2112.0
1096.0
1968.0
2
θ range for data
collection / °
6
.68 to 60.00
4.78 to 52.19°
3.74 to 60.00
5.65 to 60.00
3.74 to 60.07
-
11 ≤ h ≤ 11,
-12 ≤ h ≤ 12
-26 ≤ k ≤ 26
-30 ≤ l ≤ 30
-17 ≤ h ≤ 17
-18 ≤ k ≤ 18
-18 ≤ l ≤ 18
-12 ≤ h ≤ 12
-26 ≤ k ≤ 26
-30 ≤ l ≤ 30
-
13 ≤ h ≤ 13
index ranges
-11 ≤ k ≤ 11,
-21 ≤ l ≤ 21
-
19 ≤ k ≤ 19
-
26 ≤ l ≤ 26
65251
7292
reflections collected
independent refl.
R(int)
108584
5253
211274
10986
110478
10904
214736
10802
0.046
0.0296
0.0607
0.0347
0.0401
data/restraints/para-
meters
7
292/45/541
1.049
5253/0/319
10986/0/637
10904/0/469
10802/1/500
2
goodness-of-fit on F
1.177
1.027
1.045
1.038
R
1
/ wR
/ wR
2
[I≤2σ(I)]
0.0275 / 0.0608
0.0408 / 0.0649
0.755 / -0.549
1001351
0.0590 / 0.1630
0.0613 / 0.1641
3.38/-3.26
0.0215 / 0.0484
0.0249 / 0.0501
1.51 / -1.90
1549430
0.0201 / 0.0439
0.0227 / 0.0449
0.72 / -0.99
1549431
0.0317 / 0.0787
0.0337 / 0.0802
1.66 / -1.33
1549432
R
1
2
(all data)
-
3
Δρmax/min / e Å
CCDC number
1549429
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201702855
FULL PAPER
Königsmann, PhD thesis, Universität Bremen, Bremen, 2005; c) B.
Waerder, S. Steinhauer, B. Neumann, H.-G. Stammler, A. Mix, Y. V.
Vishnevskiy, B. Hoge, N. W. Mitzel, Angew. Chem. Int. Ed. 2014, 53,
Acknowledgements
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.
1
1640–11644; B. Waerder, S. Steinhauer, B. Neumann, H.-G.
Stammler, A. Mix, Y. V. Vishnevskiy, B. Hoge, N. W. Mitzel, Angew.
Chem. 2014, 126, 11824–11828.
[
[
10] J. Klosener, M. Wiesemann, M. Niemann, B. Neumann, H.-G.
Stammler, B. Hoge, Chem. Eur. J. 2017, 34, 8295-8303.
11] J. Landmann, F. Keppner, D. B. Hofmann, J. A. P. Sprenger, M. Häring,
S. H. Zottnick, K. Müller-Buschbaum, N. V. Ignat'ev, M. Finze, Angew.
Chem. Int. Ed. 2017, 56, 2795-2799.
[
12] a) S. Pelzer, B. Neumann, H.-G. Stammler, N. Ignat'ev, B. Hoge,
Chem. Eur. J. 2017, doi:ꢀ10.1002/chem.201700634; b) N. Schwarze, S.
Steinhauer, B. Neumann, H.-G. Stammler, B. Hoge, Angew. Chem. Int.
Ed. 2016, 55, 16156-16160.
Keywords: pentafluoroethyl • stannate(II) anion • perfluoroalkyl •
Lewis acidity • fluoride
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1]
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Chemistry - A European Journal
10.1002/chem.201702855
FULL PAPER
FULL PAPER
An acidic stannane: Introduction
of three electron withdrawing
Markus Wiesemann, Johannes
Klösener, Mark Niemann, Beate
Neumann, Hans-Georg Stammler and
Berthold Hoge*
pentafluoroethyl groups results in
a stannane, HSn(C
2 5 3
F ) , which is
fully deprotonated in water. The
-
corresponding base [Sn(C
2
F
5
)
3
]
Page No. – Page No.
exhibit remarkable stability. In this
The Tris(pentafluoroethyl)stannate(II)
contribution we present various
-
Anion [Sn(C
Reactivity
2
F
5
)
3
] – Synthesis and
-
protocols for [Sn(C
2
F
5
)
3
] -salt
formation and present the
reactivity towards carbon- and
element halides as well as
transition metal complexes.
This article is protected by copyright. All rights reserved.