Tris(pentafluoroethyl)stannane: Tin Hydride Chemistry with an Electron-Deficient Stannane

Article abstract of DOI:10.1002/chem.201705068

A versatile two-step synthesis of tris(pentafluoroethyl)stannane, HSn(C₂F₅)₃, is presented. Electron-withdrawing C₂F₅ groups significantly influence the polarity of the tin–hydrogen bond, which allows facile deprotonation of the compound, even in water. The utility of this electron-deficient stannane was illustrated in hydrostannylations of alkenes and alkynes, as well as in dehalogenation reactions. The remarkably high reactivity of HSn(C₂F₅)₃ is demonstrated in fast hydrostannylations, even in the absence of activators, whereby the regioselectivity of this process turns out to be solvent dependent. It is of great advantage that in dehalogenation reactions volatile halogenotris(pentafluoroethyl)stannanes, XSn(C₂F₅)₃ (X=I, Br), are formed that allow facile separation of the tin-containing byproducts from the reaction mixtures.

Full text of DOI:10.1002/chem.201705068

A Journal of
Accepted Article
Title: Tris(pentafluoroethyl)stannane: Tin Hydride Chemistry with an
Electron-deficient Stannane
Authors: Markus Wiesemann, Mark Niemann, Johannes Klösener,
Beate Neumann, Hans-Georg Stammler, and Berthold Hoge
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Tris(pentafluoroethyl)stannane: Tin Hydride Chemistry with an
Electron-deficient Stannane
Markus Wiesemann, Mark Niemann, Johannes Klösener, Beate Neumann, Hans-Georg Stammler and
Berthold Hoge*
Abstract:
tris(pentafluoroethyl)stannane, HSn(C
withdrawing C groups significantly influence the polarity of the tin-
A
versatile
two-step
synthesis
for
fluorinated alkyl chains were introduced into stannanes to achieve
the complete extraction of the fluorinated organotin species with
fluorinated solvents. Curran et al. impressively demonstrated the
2
5 3
F )
, is presented. Electron
2
F
5
hydrogen bond allowing facile deprotonation of the compound even in
water. The utility of this electron-deficient stannane was illustrated in
hydrostannylations of alkenes and alkynes as well as in
dehalogenation reactions. The remarkable, high reactivity of
advantage
of
such
compounds
in
dehalogenation-,
hydrostannylation and radical cyclization reactions in combination
[
10]
with a work-up by extraction.
However, the fluorinated alkyl
chain had never been attached directly to the tin center. Instead
an ethylene bridge was inserted as a spacer to mimic the
reactivity known from common tin hydrides. Moreover, the
presence of the spacer allowed the convenient preparation via
Grignard reagents.
2 5 3
HSn(C F ) is demonstrated in fast hydrostannylations, even in the
absence of activators, whereby the regioselectivity of this process
turned out to be solvent dependent. It is of great advantage that in
dehalogenation reactions volatile halogenotris(pentafluoroethyl)-
stannanes, XSn(C
2
F
5
)
3
(X = I, Br), are formed which allows a facile
In general, the incorporation of electron withdrawing groups
[
6,11]
separation of the tin containing by-products from the reaction mixtures. in tin hydrides leads to a destabilization of the Sn-H bond.
Thus, the substitution of one hydride in SnH , which is moderately
stable in the gas-phase even at ambient temperature, with a
4
[
12]
3
halide leads to the thermally instable H SnX (X = Cl, Br, I).
Introduction
An example for an isolable H-functionalized stannane
bearing electron withdrawing perfluorinated alkyl substituents was
[
1]
Dispite their toxicity and an intensive quest for appropriate
reported
tris(trifluoromethyl)stannane, HSn(CF
BrSn(CF with n-Bu SnH at low temperatures. The compound
was identified by NMR and IR spectroscopy but decomposed at
by
Eujen
et
al.
who
prepared
[
2,3]
surrogates
triorganotin hydrides remain indispensable
3 3
) ,
by reduction of
reagents in synthetic chemistry particularly for dehalogenation
3
)
3
3
[
4–7]
and hydrostannylation processes.
In general dehalogenations
cover only one aspect of a series of defunctionalizations including
deselenations, deoxygenations or deaminations. In addition the
hydrostannylation reaction represents a highly efficient strategy
for tin-carbon bond formation. The thereby obtained organotin
species are valuable starting materials for further derivatizations
[13]
room temperature.
We therefore set on to inquire whether
alternative perfluoroalkyl groups could stabilize electron poor tin
hydrides.
In some cases the replacement of a CF
3 2 5
group by a C F
unit had a benign effect on the stability of the main group element
[
8,9]
as e.g. the palladium catalyzed Stille reaction.
The most
[14–16]
alkyls while retaining the electron-deficiency.
Furthermore
frequently employed tin hydride is tri-n-butyltin hydride due to its
the introduction of perfluorinated alkyl groups is accompanied by
an increased volatility in comparison to non-fluorinated tin
derivatives, which would allow for a facile and convenient removal
[
4]
facile preparation and convenient handling.
The also
commercially available trimethyl- and triphenyltin hydrides are
[
2]
significantly more hazardous or less reactive than n-Bu
3
SnH.
[15–17]
of tin containing compounds under reduced pressure.
However, the thorough separation of tin containing by-products is
not trivial, which hampered the use of tin hydrides. Different
strategies for defunctionalization reactions were designed to
overcome these obstacles. Thus, the regeneration of tin hydrides
with phenylsilanes or polymethylhydrosiloxane (PMHS) allows the
use of only catalytic amounts of the tin containing precursors, and
therefore concomitantly less tin containing by-products are
Results and Discussion
We recently published the synthesis of novel pentafluoroethyltin
compounds by treatment of phenyl-protected tin chlorides,
[16]
Ph4-nSnCl
n
(n = 1-3), with pentafluoroethyllithium, LiC
2
F
5
.
The
[
2]
formed. In some cases the complete substitution of tin hydrides
by silicon hydrides was possible.
latter is in situ generated by combination of gaseous
pentafluoroethane, HC with n-BuLi and, unlike the
homologous LiCF , isstable up to -40 °C. Subsequent cleavage
of the phenyl groups with gaseous HBr leads to the formation of
the corresponding bromostannanes Br Sn(C 4-n (n = 1-3).
Analogous to the synthesis of the lighter congeners HSi(C
2
5
F ,
In a different approach emphasis was put on the synthesis
of readily separable organotin by-products. Thus, long partially
[18]
3
n
2 5
F )
2
5 3
F )
*
Dr. M. Wiesemann, M. Niemann, Dr. J. Klösener, B. Neumann, Dr.
H.-G. Stammler, Prof. Dr. B. Hoge
and HGe(C
of BrSn(C
2
F
5
)
3
, HSn(C was finally formed by the reduction
2
F
5
)
3
2
F
5
)
3
with n-Bu SnH in the absence of a solvent
3
Centrum für Molekulare Materialien
[
19]
Fakultät für Chemie, Universität Bielefeld,
Universitätsstraße 25, 33615 Bielefeld (Germany)
E-Mail: b.hoge@uni-bielefeld.de
(Scheme 1).
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Chemistry - A European Journal
10.1002/chem.201705068
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-
1
valence mode at 1943 cm (Figure 2) which appears at a higher
-
1
[22]
frequency than in HSn[CH(SiMe
3
)
2
]
3
(1842 cm ).
the signal of the proton
7.75 ppm) is significantly deshielded in comparison to that for
HSn[CH(SiMe (5.94 ppm) which demonstrates the electron
deficiency at the hydrogen atom.
In the
1
2 5 3
H NMR spectrum of HSn(C F )
(
Scheme 1. Tris(pentafluoroethyl)stannane formation in the reaction of the
bromo derivative with tri-n-butyltin hydride at low temperatures.
3 2 3
) ]
The product was separated in high vacuum from the reaction
mixture at -25 °C as the most volatile component, and was
collected in a cooling trap as a colorless liquid in an 83 % yield.
1
Its H NMR spectrum exhibits a complex multiplet at 7.75 ppm
due to extensive coupling of the proton to the fluorine atoms of
the C
2 5
F units. In addition, this resonance is decorated with tin
1
117/119
satellites with a J(H,
Sn) coupling constant of 2464/2582 Hz.
The F NMR spectrum is characterized by a singlet at -83.9 ppm
for the CF groups and a doublet at -110.5 ppm with tin satellites
1
9
3
2
117/119
(
J(F,
Sn) = 336/353 Hz) for the CF
2
groups. The doublet is
J(F,H) coupling of 8 Hz. Accordingly, the
spectrum displays doublet
3
caused by
a
1
19
19
Sn{ F} NMR
a
1
119
2
119
(
J( Sn,H) = 2588 Hz) whereas a septet ( J( Sn,F) = 349 Hz)
3
119
of decets ( J( Sn,F) = 8 Hz) at -267.8 ppm is observed in the
1
19
1
Sn{ H} NMR spectrum.
2 5 3
Figure 2. IR spectrum of HSn(C F ) in the gas phase.
A single crystal suitable for X-ray diffraction was grown in
situ in a capillary at -72 °C. HSn(C
monoclinic space group P2 /n. The structural analysis reveals the
presence of molecule belonging to the rare class of
triorganostannanes HSnR . Moreover, HSn(C is the only
2 5 3
F ) crystallizes in the
As proven recently by multinuclear NMR spectroscopy the
solvation of HSn(C in pure water leads to a complete
dissociation under
tris(pentafluoroethyl)stannate(II) anion. Additionally, a pK
1
a
2 5 3
F )
F
5
)
3
formation
of
the
3
2
known structurally characterized example of a triorganostannane
featuring electron withdrawing groups.
a
value
of 0.8 was determined by titration with NaOH in aqueous
isopropanol, which nicely emphasized the distinct effect of the
[
23]
perfluorinated substituents on the acidity of Sn-H bonds.
Although the synthesis of HSn(C from BrSn(C
SnH is selective, this protocol is not recommendable. The
preparation of BrSn(C requires a multi-step protocol, and the
subsequent liberation of an equimolar amount of hazardous n-
Bu SnBr impeded a broad application and upscaling. A more
2
F
5
)
3
2 5 3
F ) and
n-Bu
3
2
5 3
F )
3
direct procedure for this stannane was therefore highly desirable.
We recently reported on the synthesis of salts comprising the
-
tris(pentafluoroethyl)stannate(II) anion, [Sn(C
2
F
5
)
3
] , by direct
pentafluoroethylation of tin(II) chloride (Scheme 2). Subsequent
salt metathesis with [PPh ]Cl afforded the isolable
tetraphenylphosphonium salt, [PPh
4
4
][Sn(C
2
F
5
)
3
] in a one-pot
[
23]
synthesis on a multigram scale.
This makes the preparation of HSn(C
][Sn(C
For a subsequent workup we tested different setups with low
2
F
5 3
) by protonation of
[
PPh
4
2 5 3
F ) ] with strong Brønstedt acids conceivable.
2 5 3
Figure 1. Molecular structure of tris(pentafluoroethyl)stannane, HSn(C F ) .
volatile solvents and acids. As solvents n-decane, 1,6-
dichlorohexane and 1,6-dibromohexane were used in
combination with hydrochloric, sulfuric and trifluoromethylsulfonic
acid. The best results were obtained by the addition of
Thermal ellipsoids are shown at 50 % probability. Selected bond lengths [pm]
and angles [°]: Sn1-C1 220.5(3), Sn1-C3 220.9(3), Sn1-C5 220.3(3), Sn1-H1
1
58(4), C1-Sn1-C3 107.1(1), C1-Sn1-C5 107.2(1), C3-Sn1-C5 106.6(1), H1-
Sn1-C1 114.2(13), H1-Sn1-C3 111.5(12), H1-Sn1-C5 109.9(13).
trifluoromethylsulfonic acid to a slurry of [PPh
dibromohexane at 0 °C, which yielded 9 g of the pure product
71 %). In all other cases the yields were significantly lower due
to decomposition of the crude product. Pure HSn(C is not
stable at room temperature and decomposes slowly under H
elimination to produce hexakis(pentafluoroethyl)distannane,
4 2 5 3
][Sn(C F ) ] in 1,6-
The average C-Sn-C angle in HSn(C
2 5 3
F ) (107°) is considerably
(
more acute than the corresponding angle for the electron rich
2
5 3
F )
[
20]
stannane HSn[CH(SiMe
concept and Bent’s rule electron withdrawing substituents (e.g.
) require less space than electron rich substituents (e.g.
3
)
2
]
3
(113°).
According to the VSEPR
2
2 5
C F
(
C
2
F
5
)
3
SnSn(C
2 5 3
F ) , selectively. Similar to the degradation of
[
21]
3 2 2 5 3 s
CH(SiMe ) ). The IR spectrum of HSn(C F ) exhibits a n (SnH)
SnH
4
the rate constant of this process strongly depends on small
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amounts of unknown impurities. Whereas a degradation of pure
probably due to a hindered rotation of the ethylene unit. A
simulation as an AA’BB’X spinsystem allowed the determination
2 5 3
samples of HSn(C F ) requires days at ambient temperature the
3
3
crude product and impure material decompose within minutes.
of the J(H
A B A
,H )- (12.0 Hz) and J(H ,HB’) coupling constants
(
5.4 Hz) (Figure 3).
Scheme 2. Synthesis of tris(pentafluoroethyl)stannane via protonation of
[
4 2 5 3
PPh ][Sn(C F ) ].
In conclusion, our improved protocol now allows the generation of
HSn(C on a multigram scale and facilitates a further insight
into the chemistry of this perfluorinated and thus electron-deficient
2
5 3
F )
stannane. At first we investigated the reactivity of HSn(C
2
F
5
)
3
in
a
1
Figure 3. Segment of the
(
H NMR spectrum of 2-phenylethyltris-
[26]
hydrostannylation reactions of styrene derivatives, with
pentafluoroethyl)stannane (top) and simulated spectrum (bottom, gNMR )).
particular focus on regioselectivity. Basically the Sn-H-
functionality in organotin hydrides is amphiphilic and thus may
Just the signals for the ethylene protons are shown.
[
8]
display protic, hydridic as well as radical features. In comparison
to the reaction of HBr with alkenes, which furnishes the a-product
due to a mesomeric stabilization of the cationic intermediate, the
b-Addition was also observed in varying amounts between
HSn(C
spectroscopic evidence for the formation of the a-product
Scheme 3). In CHCl as a more polar medium, however, the a-
2 5 3 2 2
F ) and CH =CPh in n-pentane but there was also NMR
behavior of the HSn(C
2 5 3
F ) as a Brønsted acid should be similar.
On the other hand radical intermediates or concerted reactions
(
3
[
7,24]
should deliver the b-product.
In the reaction of
product was exclusively formed, which points to different reaction
1
tris(pentafluoroethyl)stannane with styrene in n-pentane the b-
pathways in dependence of the solvent. The H NMR of the a-
product was selectively formed indicating that an initial
product gives rise to a singlet for a methyl group at 2.32 ppm with
3
117/119
protonation of the alkene by HSn(C
2 5 3
F ) is less likely in this case
tin satellites ( J(H,
Sn) = 119/124 Hz). The NMR spectrum is
CSn(C of a
(
Scheme 3). The same result was observed in the more polar
consistent with the X-ray structure of MePh
2
2 5 3
F )
chloroform. The reaction was completed within hours at room
temperature even in the absence of radical starters or transition
metal catalysts. This underlines the remarkably high reactivity of
crystal grown in situ at 17.2 °C comprising a distorted tetrahedron.
This underlines the creation of a quaternary carbon center despite
the steric congestion conferred by the phenyl rings and the
stannyl unit (Figure 4).
[
25]
2 5 3
HSn(C F ) .
Scheme 3. Hydrostannylation of styrene and 1,1-diphenylethylene in n-pentane
3
or CHCl .
1
The H NMR spectrum of PhCH
2
CH
2
Sn(C
2
F
5
)
3
reveals two
signals for the ethylene group at 3.07 and 2.20 ppm, each
3
2
decorated with tin satellites ( J(H,Sn) = 65 Hz, J(H,Sn) = 59 Hz).
Instead of the expected triplet for the enantiotopic hydrogen
atoms both signals are characterized by a complex multiplet
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Chemistry - A European Journal
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Figure 4. Molecular structure of MePh
shown at 50 % probability. Selected bond lengths [pm] and angles [°]: Sn1-C1
2
CSn(C
2
F
5
)
3
. Thermal ellipsoids are
C2 133.3(2), Sn1-C1-C2 126.9(1), C1-C2-C3 126.9(1), Sn1-C1-C2-C3 -3.0(2),
C1-C2-C3-C4 139.9(1).
2
9
22.8(1), Sn1-C3 223.1(1), Sn1-C5 222.5(1), Sn1-C7 219.7(1), C1-Sn1-C3
7.3(1), C1-Sn1-C5 107.1(1), C1-Sn1-C7 112.0(1), C3-Sn1-C5 101.7(5), C3-
Sn1-C7 119.3(5), C5-Sn1-C7 117.1(1).
Next we looked at the potential of HSn(C
2
F
5
)
3
as
a
dehalogenation reagent for alkyl halides. In general a distinct rate
dependence on the nature of the halide is observed. Alkyl iodides
are more readily dehalogenated than bromide and chloride
Given the facility of hydrostannylations of alkenes we set on to
determine whether alkynes could likewise be hydrostannylated.
Addition of tris(pentafluoroethyl)stannane to a chloroform solution
of phenylacetylene selectively led to the formation of a single
[
4,27]
derivatives (I > Br > Cl).
reactivity we treated a 1:1:1 mixture of 1,6-diiodo-, 1,6-dibromo-
and 1,6-dichlorohexane in chloroform with HSn(C and
monitored the reaction by NMR spectroscopy (Scheme 5).
As an illustration of this gradual
1
2 5 3
F )
product. In the H NMR spectrum two signals for the alkene
protons at 8.16 and 6.06 ppm with tin satellites
3
2
3
(
J(H,Sn) = 275/287 Hz; J(H,Sn) = 145/152 Hz) and a J(H,H)
coupling constant of 11 Hz agree with a formation of the cis-b-
product (Scheme 4).
2 5 3
Scheme 5. Reaction of 1,6-dihalidohexane with HSn(C F ) .
1
9
In previous experiments the F NMR spectra of the possible
products ISn(C , BrSn(C , ClSn(C exhibit resonances
for the CF group with markedly different J(F, Sn) coupling
Scheme 4. Hydrostannylation of phenylacetylene.
2
F
5
)
3
2
F
5
)
3
2 5 3
F )
2
119
2
2
2
2 5 3
constants ( J(F,Sn) = 422 Hz for ISn(C F ) , J(F,Sn) = 447 Hz
This assignment was confirmed by an X-ray diffraction study with
single crystals grown in situ at -20.2 °C in a glas capillary. The
molecule displays a cis-oriented 1,2-disubstituted olefin with a
C1-C2 bond length of 133.3(2) ppm. The orientation of the atoms
Sn1, C1, C2 and C3 is close to planarity (torsion angle 3.0(2)°).
The phenyl ring deviates from this plane by about 40°, presumably
caused by severe steric congestion.
2
[16]
1
for BrSn(C
NMR spectrum the terminal halomethyl groups give rise to distinct
signals at 3.50 for CH Cl, 3.37 for CH Br and 3.15 ppm for CH
Figure 6). When two equivalents of HSn(C were added to
this 1:1:1 mixture a complete conversion was observed with
2 5 3 2 5 3
F ) , J(F,Sn) = 461 Hz for ClSn(C F ) ). In the H
2
2
2
I
(
2 5 3
F )
1
2 5 3
ISn(C F ) as the exclusive organotin species. In the H NMR
spectrum of the crude product mixture the signals for 1,6-
diiodohexane disappeared while the ratio of the 1,6-dibromo and
In conclusion, these first hydrostannylation reactions of
alkenes and alkynes in the absence of additives and a predictable
solvent-depending regioselectivity are a promising requisite for a
1
,6-dichlorohexane remained unchanged (Figure 6).
general
and
broadly
applicable
synthesis
of
tris(pentafluoroethyl)tin compounds.
1
Figure 6. Part of the H NMR spectrum of the crude product mixture of 1,6-
diiodo-, 1,6-dibromo- and 1,6-dichlorohexane (ratio 1:1:1) before (top) and after
(
2 5 3
bottom) treatment with HSn(C F ) (X = Cl, Br, I).
Figure
5.
Molecular
structure
Sn(C
of
(Z)-2-phenylethen-1-yl-
tris(pentafluoroethyl)stannane, PhC
2
H
2
2
F
5
)
3
. Thermal ellipsoids are shown
However, debromination with a third equivalent HSn(C
turned out to be impossible in the presence of ISn(C because
of the competing formation of the symmetrical distannane
2
5 3
F )
at 50 % probability. Selected bond lengths [pm] angles [°] and torsion angles [°]:
Sn1-C1 210.6(1), Sn1-C9 221.7(1), Sn1-C11 221.9(1), Sn1-C13 221.8(1), C1-
2
5 3
F )
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Chemistry - A European Journal
10.1002/chem.201705068
Full Paper
(
F
5
C
2
)
3
SnSn(C
2
F
5
)
3
.
Compared to tri-n-butyltin halides
(X = Cl, Br, I), have
2 5 3
The chemoselectivity of reactions with HSn(C F ) remains
tris(pentafluoroethyl)tin halides, XSn(C
2
F
5
)
3
intriguing. First orientating answers were expected from the
behavior of the stannane towards bifunctional reactants like 4-
bromostyrene, allyl bromide and 6-bromo-1-hexene. The
exposure of 4-bromostyrene to an n-pentane solution of
much higher vapor pressures (7 to 25 mbar) and are thus
conveniently removed under reduced pressure at room
[
16]
temperature.
Again it should be highlighted that there is no
need for a radical starter like azobisisobutyronitrile (AIBN). Clearly
perfluoroalkyl substituents activate the Sn-H functionality
sufficiently to undergo addition and substitution reactions.
An independent synthesis of the novel iodostannane
HSn(C
2
F
5
)
3
selectively
afforded
2-(4-
bromophenyl)ethyltris(pentafluoroethyl)stannane. In contrast to
this, allyl bromide and 6-bromo-1-hexene are cleanly
debrominated by the tin hydride with retainment of the C=C-
double bond. A competitive test reaction of cyclohexyl bromide
ISn(C
tris(pentafluoroethyl)stannane with iodine. The compound was
isolated and like its homologues BrSn(C and ClSn(C it
forms a crystalline complex with 1,10-phenanthroline (phen)
2
F
5
)
3
was
devised
from
the
treatment
of
and ethyl acrylate with HSn(C
2
F
5
)
3
in chloroform clearly
2
F
5
)
3
2 5 3
F )
demonstrated a preference for hydrostannylation to give ethyl 3-
tris(pentafluoroethyl)stannylpropionate,
bromide remained unaffected (Scheme 7).
whereby
cyclohexyl
[
16]
(
Scheme 6). A crystal suitable for X-ray diffraction was grown
from a dichloromethane solution (Figure 7).
2 5 3
Scheme 6. Oxidation of HSn(C F ) with iodine and complexation of the formed
iodotris(pentafluoroethyl)stannane with 1,10-phenanthroline.
2 5
The molecule displays an octahedral geometry with the C F
groups in a meridional position and nearly identical Sn-C bond
2 5 3
Scheme 7. Reactions of HSn(C F ) with bromoalkenes and -alkanes in n-
1
9
lengths of about 228 pm. The F NMR spectrum of the complex
shows two sets of signals for the inequivalent C groups in the
ration of 2:1. The resonances of the CF groups at -118.6
pentane.
2
F
5
2
2
and -112.1 ppm are decorated with tin satellites ( J(F,Sn) = 516
and 305 Hz, respectively).
Conclusions
In this contribution we present
a
two-step synthesis for
5 3
F ) , as a rare example of
tris(pentafluoroethyl)stannane, HSn(C
2
an electron-deficient stannane. Due to the electron withdrawing
effect of the pentafluoroethyl groups a protic polarization is
exerted on the Sn-H bond. Unlike other tin hydrides HSn(C
acts as a Brønsted acid (pK = 0.8) which is deprotonated even
with water. At room temperature solutions of HSn(C as well
as the pure substance slowly decompose to selectively afford
2 5 3
F )
a
[
23]
2
5 3
F )
hexakis(pentafluoroethyl)distannane, (F
5
C
2
)
3
SnSn(C
2
F
5
)
3
.
We
in
investigated the chemical behavior of HSn(C
2
F
5
)
3
hydrostannylation as well as dehalogenation reactions. In the
former case the hydrostannylations of styrene, 1,1-
diphenylethylene and phenylacetylene were completed within
hours even in the absence of additives which emphasizes the
2 5 3
remarkable reactivity of HSn(C F ) . Its regioselectivity in the
reaction with 1,1-diphenylethylene is solvent dependent
preferring the sterically disfavored a-addition product in more
3
polar solvents such as CHCl . The dehalogenation reaction
Figure
phenanthrolinetin(IV), [SnI(C
probability. Selected bond lengths [pm] and angles [°]: Sn1-I1 278.9(1), Sn1-C1
7.
Molecular
structure
of
iodotris(pentafluoroethyl)-1,10-
discloses an decreasing rate in the series I > Br > Cl. This allows
for a selective deiodation of alkyl iodides in the presence of alkyl
2
5 3
F ) (phen)]. Thermal ellipsoids are shown at 50 %
2
2
9
28.2(1), Sn1-C3 228.3(1), Sn1-C5 227.4(1), Sn1-N1 233.6(1), Sn1-N2
31.8(1), I1-Sn1-C1 102.1(1), I1-Sn1-C3 88.2(1), I1-Sn1-C5 87.9(1), I1-Sn1-N2
5.1(1), N1-Sn1-N2 71.9(1).
bromides
iodotris(pentafluoroethyl)stannane may also be prepared by
direct oxidation of HSn(C with elemental iodine. In
and
alkyl
chlorides.
The
novel
2
5 3
F )
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201705068
Full Paper
+
+
∙+
∙+
competitive reactions of HSn(C
2
F
5
)
3
with 4-bromostyrene, allyl
[HSnF
2
] , 139.0 (76) [SnF] , 120.0 (13) [Sn] , 100.0 (100) [C
2
F
4
] , 69 (37)
+
~
[
CF
3
] ; IR (gas phase): n=1943 (w), 1322 (s), 1301 (m), 1222 (s), 1122 (s),
bromide, cyclohexyl bromide, ethyl acrylate and 6-bromo-1-
hexene we discovered that only in the case of activated double
bonds hydrostannylation is favored over debromination. In no
case C-C bond formation as an indication for radical intermediates
was observed.
-
1
9
40 (s), 742 (m), 528 (m) cm .
Synthesis
of
tetraphenylphosphoniumtris(pentafluoroethyl)-
stannate(II): HC
2
F
5
(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,
.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
(
5
Experimental Section
4
crude product suspension. After stirring for 48 h at room temperature the
precipitate was filtered off and the solvent was removed under reduced
pressure. After recrystallization from chloroform/n-pentane the product
All chemicals were obtained from commercial sources and used without
further purification. Standard high-vacuum techniques were employed
throughout all preparative procedures. Non-volatile compounds were
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),
handled in a dry N
2
atmosphere using Schlenk techniques. NMR spectra
1
3
1
1
7.76 (m, 8H; Ar-H), 7.61 ppm (m, 8H; Ar-H); C{ H} NMR ([D]chloroform,
were recorded on a Bruker Model Avance III 300 spectrometer ( H 300.13
4
2
1
9
31
119
13
298 K): d=135.8 (d, J(C,P)=3 Hz; para-C), 134.3 (d, J(C,P)=10 Hz; ortho-
MHz; F 282.40 MHz; P 121.49 MHz; Sn 111.92 MHz; C 75.47 MHz)
with positive shifts being downfield from the external standards (85 %
3
1
C), 130.7 (d, J(C,P)=13 Hz; meta-C), 117.4 ppm (d, J(C,P)=90 Hz; ipso-
1
3
19
3
1
19
13
1
119
C);
1
C{ F}
J(C,Sn)=526/548 Hz; CF
NMR ([D]chloroform, 298 K): d=-83.0 (m,
NMR
([D]chloroform,
298 K):
d=135.9
(s,
orthophosphoric acid ( P), CCl
NMR spectra were recorded in the indicated deuterated solvent or in
relation to [D ]acetone filled capillaries. IR spectra were recorded on an
3
F ( F), TMS ( C, H), SnMe
4
(
Sn).
2
19
2
), 122.3 ppm (s, J(C,Sn)=19 Hz; CF
3
);
F
3
J(F,Sn)=61 Hz, 9F;
6
2
31
1
CF
3
), -117.5 ppm (m, J(F,Sn)=117 Hz, 6F; CF
2
);
P{ H} NMR
ALPHA-FT-IR spectrometer (Bruker). ESI mass spectra were recorded
using an Esquire 3000 ion-trap mass spectrometer (Bruker Daltonik
GmbH, Bremen, Germany) equipped with a standard ESI/APCI source. 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. Elemental analyses were
1
3
(
2
[D]chloroform, 298 K): d=23.3 (s, J(C,P)=90 Hz, J(C,P)=13 Hz,
119
1
J(C,P)=10 Hz);
Sn{ H} NMR ([D]chloroform, 298 K): d=-163.7 ppm
2
3
119
19
(
(
sept, dec, J(Sn,F)=119 Hz, J(Sn,F)=63 Hz);
[D]chloroform, 298 K): d=-163.7 ppm (s).
Sn{ F} NMR
recorded
010. Melting points were measured on a Mettler Toledo Mp70 Melting
Point System. Vapor pressures were determined with VAP 5
Vacuubrand), a piezo vacuum gauge. The crystal data were collected
on
a
EURO
EA
Element
Analyzer
Synthesis of tris(pentafluoroethyl)stannane from [PPh ][Sn(C
4
2 5 3
F ) ]:
2
HSO CF (5.02 g, 33.42 mmol) was added to [PPh ][Sn(C F ) ] (22.56 g,
3
3
4
2 5 3
a
27.68 mmol) in 1,6-dibromohexane (40 mL) at 0 °C. An instantaneous
hydrogen generation was observed. While the suspension was allowed to
reach room temperature all volatile compounds were condensed in a
cooling trap (-196 °C). The raw product was purified by isothermal
distillation at 0 °C with a vapor pressure of 15 mbar. The product was
(
a
using Mo-K radiation (l = 71.073 pm). The crystals were kept at 100.0(1)
[
29]
K during data collection. Using Olex2
the structures were solved and
[
30]
refined with the ShelX program package using direct methods and least-
squares minimization. Single crystals of HSn(C were in situ grown at
01 K by manually generating a suitable crystal seed and afterward chilling
to 100 K with 50 K/h. At ca. 169 K a phase transition from an orthorhombic
phase with heavy disordered C ligands to the here described non-
disordered monoclinic twinned crystal with two domains (ratio 81:19) can
be obtained. Single crystals of MePh CSn(C were in situ grown at
90.3 K, chilling to 287.0 K with 2 K/h and to 100 K with 50 K/h. Single
crystals of PhC Sn(C were in situ grown at 252 K, chilling to 242 K
1
2
F
5
)
3
obtained as a colorless liquid (9.35 g, 19.61 mmol, 71 %). H NMR
1
2
(neat/[D
6
]acetone, 298 K): d=7.53 ppm (m, J(H,Sn)=2443/2555 Hz, 1H);
1
9
F NMR (neat/[D
6
]acetone, 298 K): d=-85.4 (s, 9F; CF
3
), -111.8 ppm (d,
3
2
2
F
5
J(F,H)=9 Hz, J(F,Sn)=335/352 Hz, 6F; CF ).
2
2
2 5 3
F )
Synthesis of 2-phenylethyltris(pentafluoroethyl)stannane: Styrene
2
(0.30 g, 2.88 mmol) was condensed onto a solution of HSn(C F ) (1.22 g,
2
5 3
2
H
2
2
F
5
)
3
2.56 mmol) in chloroform (5 mL). The solution was stirred for 2.5 h at room
-
with 10 K/h and to 100 K with 50 K/h. Details of the X-ray investigation are
given in Table. 1. CCDC 1001350 and 1565485-1565487 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.
temperature. Removing all volatile compounds at high vacuum (1x10
3
mbar) furnished the product as a slightly turbid liquid (1.15 g, 1.98 mmol,
1
77 %). H NMR ([D]chloroform, 298 K): d=7.42-7.20 (m, 5H; Ar-H), 3.07
3
3
(
AA’BB’X
spin
system,
J(H
A
H
B
)=12.0 Hz,
A
J(H HB’)=5.4 Hz,
3
3
1
J(H,Sn)=65 Hz, 2H; PhCH ), 2.20 ppm (AA’BB’X spin system,
2
3
2
J(H
A
1
H
B
)=12.0 Hz, J(H
A
H
B’)=5.4 Hz, J(H,Sn)=59 Hz, 2H; SnCH
2
);
3
3
Synthesis
Bromotris(pentafluoroethyl)stannane, BrSn(C
was condensed onto n-Bu SnH, (4.02 g, 13.81 mmol) at -196 °C. The
of
tris(pentafluoroethyl)stannane:
C{ H} NMR ([D]chloroform, 298 K): d=141.5 (s, J(C,Sn)=87/91 Hz; ipso-
2
F
5
)
3
, (7.49 g, 13.48 mmol)
C), 129.1 (s; arom. C), 127.6 (s, arom. C), 127.2 (s; arom. C), 30.4 (s,
2
1
13
19
3
J(C,Sn)=28 Hz; PhCH
2
), 17.1 ppm (s, J(C,Sn)=355 Hz; SnCH
2
); C{ F}
),
1
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 -
NMR ([D]chloroform, 298 K): d=125.4 (s, J(C,Sn)=457/477 Hz; CF
2
2
19
119.4 ppm (s, J(C,Sn)=75/78 Hz; CF
3
); F NMR ([D]chloroform, 298 K):
-
3
2
119
1
1
96 °C cooling trap in a dynamic high vacuum (10 mbar). The product
was kept at temperatures below -60 °C to prevent decomposition.
HSn(C was obtained as a colorless liquid (5.27 g, 11.05 mmol, 82 %).
Vapor pressure (22 °C): 30mbar.
d=-83.0 (s, 9F; CF
3
), -111.3 ppm (s, J(F,Sn)=297 Hz, 6F; CF
2
); Sn{ H}
2
NMR ([D]chloroform, 298 K): d=-166.5 ppm (sept, J(Sn,F)=305 Hz);
1
19
19
3
2
F
5
)
3
Sn{ F} NMR ([D]chloroform, 298 K): d=-166.5 ppm (t, t, J(Sn,H)=67 Hz,
J(Sn,H)=59 Hz).
1
2
H
NMR ([D]chloroform, 298 K):
1
13
19
d=7.75 ppm (m, J(H,Sn)=2464/2582 Hz, 1H; SnH);
C{ F} NMR
2
1
(
[D]chloroform, 298 K): d=124.4 (d, J(C,H)=19 Hz, J(C,Sn)=590/617 Hz;
Synthesis of 1,1-diphenyleth-1-yltris(pentafluoroethyl)stannane:
2
19
CF
2
), 119.0 ppm (s, J(C,Sn)=83 Hz; CF
3
); F NMR ([D]chloroform,
HSn(C F ) (0.95 g, 1.99 mmol) was condensed onto a solution of 1,1-
2
5 3
3
2
2
98 K): d=-83.9 (s, 9F; CF
3
), -110.5 ppm (d,
J(F,H)=8 Hz,
diphenylethylene (0.34 g, 1.89 mmol) in chloroform (5 mL). The solution
was stirred for 1 h at room temperature. Removing all volatile compounds
in high vacuum furnished the product as a colorless liquid (1.19 g,
1.81 mmol, 96 %). M.p.: 18 °C. Crystals suitable for X-ray diffraction were
119
1
2
J(F,Sn)=336/353 Hz, 6F; CF ); 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,
+
1
7
2 5
0 eV, pos.) {m/z (%) [assignment]}: 259.0 (47) [HSnF(C F )] , 159.0 (22)
grown by in situ crystallization in a capillary. H NMR ([D]chloroform,
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201705068
Full Paper
3
4
3
2
98 K): d=7.45-7.15 (m, 10H; Ar-H), 2.32 ppm (s, J(H,Sn)=119/124 Hz,
J(H,H)=1.5 Hz, 2H; H4/H7), 8.34 (s, 2H; H5/H6), 8.29 ppm (dd,
1
3
1
3
13
1
3
3
H; CH
3
);
C{ H} NMR ([D]chloroform, 298 K): d=143.2 (s,
J(H,H)=8.3 Hz,
J(H,H)=5.2 Hz,
2H;
H3/H8);
C{ H}
NMR
4
J(C,Sn)=37 Hz; ipso-C), 129.4 (s, J(C,Sn)=12 Hz; arom.C), 128.1 (s,
([D
3
]acetonitrile, 298 K): d=149.6/149.5 (s, t, J(C,F)=7 Hz; C2/C9),
J(C,Sn)=48 Hz; arom. C), 128.0 (s; arom. C), 65.7 (m; SnCPh
2
), 27.3 ppm
143.4/143.3 (2 s; C4/C7), 138.0/137.1 (2 s; C11/C12), 130.2/130.1 (2 s;
C4a/C6a), 128.0/127.8 (2 s; C5/C6), 126.3/125.7 ppm (2 s; C3/C8);
2
13
19
(
(
s, J(C,Sn)=24 Hz; CH
3
); C{ F} NMR ([D]chloroform, 298 K): d=126.9
1
2
13
19
1
s, J(C,Sn)=321/335 Hz; CF
2
), 119.3 ppm (s, J(C,Sn)=68/73 Hz; CF
), -107.4 ppm (s,
Sn{ H} NMR ([D]chloroform, 298 K): d=-
3
);
C{ F} NMR ([D
3
]acetonitrile, 298 K): d=127.7 (s, J(C,Sn)=384/402 Hz;
), 120.6 (s; CF ), 120.1 ppm
]acetonitrile, 298 K): d=-80.2 (m,
1
9
1
F NMR ([D]chloroform, 298 K): d=-82.4 (s, 9F; CF
3
CF
2
2
), 124.0 (s, J(C,Sn)=1144/1197 Hz; CF
2
3
2
119
1
19
J(F,Sn)=265 Hz, 6F; CF
2
);
(s, J(C,Sn)=140 Hz; CF
3F; CF ), -81.8 (m, 6F; CF
118.6 ppm (m,
([D
[assignment]}: 484.7 (8) [ISn(C
3 3
); F NMR ([D
2
119
19
2
2
2
54.1 ppm (sept, J(Sn,F)=272 Hz);
Sn{ F} NMR ([D]chloroform,
3
3
), -112.1 (m, J(F,Sn)=305 Hz, 2F; CF
2
), -
3
2
119
19
98 K): d=-254.0 ppm (q, m, J(Sn,H)=123 Hz); MS (EI, 70 eV, pos.) {m/z
2
J(F,Sn)=516 Hz, 4F; CF );
Sn{ F} NMR
+
∙+
(
%) [assignment]}: 181.1 (100) [MePh
2
+
C] , 166.0 (95) [Ph
2
C] , 165.0 (85),
3
]acetonitrile, 298 K): d=-585.3 ppm (s); MS (EI, 70 eV, pos.) {m/z (%)
+
+
+
+
1
38.9 (20) [SnF] , 103 (85) [PhC
2
H
2
] , 77.0 (36) [Ph] ; elemental analysis
2
F
5
)
2
] , 384.7 (26) [ISnF(C
2
F
5
)] , 284.7 (3)
+
+
∙+
calcd (%) C20
H
13
F
15Sn: C 36.6, H 2.0; found: C 37.0, H 2.18.
[ISnF
2
+
] , 246.7 (16) [SnI] , 180.0 (100) [phen] , 154.0 (16), 138.8 (15)
~
[
SnF] ; IR (ATR): n=2962 (w), 2924 (w), 2854 (w), 1528 (w), 1435 (w),
1
297 (w), 1260 (m), 1201 (m), 1071 (s), 1017 (s), 914 (m), 868 (m), 846
Synthesis of (Z)-2-phenylethen-1-yl-tris(pentafluoroethyl)stannane:
Phenylacetylene (0.28 g, 2.74 mmol) was added to sample of HSn(C
0.68 g, 1.43 mmol) in chloroform (10 mL). After stirring for 2.5 h at room
-
1
(
m), 796 (s), 721 (m), 646 (w), 598 (w), 585 (w), 531 (w), 422 (m) cm .
2 5 3
F )
(
temperature all volatile compounds were removed in high vacuum to
obtain the product as a yellow oil (0.50 g, 0.86 mmol, 60 %). Crystals
suitable for X-ray diffraction were grown by in situ crystallization in a
Synthesis
of
2-(4-bromophenyl)eth-1-yltris(pentafluoroethyl)-
2 5 3
F ) (1.00 g, 2.10 mmol) was condensed onto a solution
stannane: HSn(C
of 4-bromostyrene (0.50 g, 2.71 mmol) in n-pentane (10 mL). The solution
was stirred for 48 h at ambient temperature. Removing all low volatile
compounds under reduced pressure furnished the oily raw product. After
1
3
capillary. H NMR ([D]chloroform, 298 K): d=8.16 (d, J(H,H)=11 Hz,
3
J(H,Sn)=275/287 Hz, 1H; PhCH), 7.46 (m, 3H; Ar-H), 7.27 (m, 2H; Ar-H),
3
2
13
1
-3
6
.06 ppm (d, J(H,H)=11 Hz, J(H,Sn)=145/152 Hz, 1H; SnCH); C{ H}
distillation (54 °C at 1x10 mbar) the product was obtained as a colorless
1
NMR ([D]chloroform, 298 K): d=156.5 (s; PhCH), 139.5 (s, J(C,Sn)=50 Hz;
arom. C), 130.2 (s; arom. C), 129.7 (s; arom. C), 125.7 (s, J(C,Sn)=10 Hz;
liquid (0.80 g, 1.21 mmol, 58 %). H NMR ([D]chloroform, 298 K): d=7.49
3
3
(d, m, J(H,H)=8.5 Hz, 2H; Br-CCH), 7.10 (d, m, J(H,H)=8.5 Hz, 2H; o-
1
13
19
3
2
arom. C), 115.8 ppm (s, J(C,Sn)=581 Hz; SnCH); C{ F} NMR
CH), 3.00 (m, J(H,Sn)=62 Hz, 2H; CH
2
), 2.12 ppm (m, J(H,Sn)=59 Hz,
C{ H} NMR ([D]chloroform, 298 K): d=140.4 (s,
J(C,Sn)=90/93 Hz; ipso-C), 132.1 (s; arom. C), 129.3 (s; arom. C), 121.1
1
13
1
(
[D]chloroform, 298 K): d=125.2 (m,
J(C,Sn)=537/557 Hz; CF
2
),
2
2H; CH );
2
19
3
1
19.4 ppm (s, J(C,Sn)=80/83 Hz; CF
3
); F NMR ([D]chloroform, 298 K):
2
2
d=-82.6 (s, 9F; CF
1
3
), -110.8 ppm (s, J(F,Sn)=312/325 Hz, 6F; CF
([D]chloroform, 298 K): d=-222.7 ppm (sept,
Sn{ F} NMR ([D]chloroform, 298 K): d=-222.7 ppm
2
);
(s; arom. C), 29.9 (s,
J(C,Sn)=26 Hz; CH
2
), 16.5 ppm (s,
19
1
1
13
19
Sn{ H}
NMR
J(C,Sn)=353 Hz; CH
J(C,Sn)=463/485 Hz; CF
2
); C{ F} NMR ([D]chloroform, 298 K): d=125.4 (s,
2
119
19
1
2
19
J(Sn,F)=326 Hz);
2
), 119.4 ppm (s, J(C,Sn)=75/78 Hz; CF
3
);
F
3
2
(
d, d, J(Sn,H)=287 Hz, J(Sn,H)=152 Hz); MS (EI, 70 eV, pos.) {m/z (%)
NMR ([D]chloroform, 298 K): d=-82.9 (s, 9F; CF
3
), -111.1 ppm (s,
∙
+
2
119
1
[
[
[
assignment]}:
578.8
(6)
[PhC
2
H
2
Sn(C
SnF(C
Sn] , 196.9 (9) [PhSn] , 164.0 (13),
2
F
5
)
3
] ,
460.8
(16)
2
J(F,Sn)=295/306 Hz, 6F; CF ); Sn{ H} NMR ([D]chloroform, 298 K): d=-
+
+
2
119
19
PhC
PhC
2
2
H
H
2
2
Sn(C
2
F
+
5
)
2
] , 360.9 (13) [PhC
2
H
2
2
F
5
)] , 260.9 (20)
167.7 ppm (sept, J(Sn,F)=305 Hz);
Sn{ F} NMR ([D]chloroform,
+
+
3
2
SnF
2
] , 222.9 (7) [PhC
2
H
2
298 K): d=-167.7 ppm (t, t, J(Sn,H)=60 Hz, J(Sn,H)=59 Hz); MS (EI,
+
+
+
∙+
1
38.9 (17) [SnF] , 103.0 (100) [PhC
2
H
2
] , 77 (23) [Ph] .
70 eV, pos.) {m/z (%) [assignment]}: 659.9 (5) [BrC
6
H
4
C
2
H
4
Sn(C
2 5 3
F ) ] ,
+
+
5
1
40.9 (13) [BrC
6
H
4
C
2
H
4
+
Sn(C
2
F
5
)
2
] , 440.9 (7) [BrC
6
H
4
C
2
H
4
SnF(C F )] ,
2 5
∙+
+
83.0 (85) [BrC H C H ] , 138.9 (14) [SnF] , 104.1 (100) [C H C H ] , 77
6 4 2 4 6 4 2 4
Synthesis of iodotris(pentafluoroethyl)stannane:
HSn(C (2.48 g, 5.20 mmol) was condensed onto a suspension of
A
sample of
+
~
(
27) [Ph] ; IR (ATR): n= 3031 (w), 2941 (w), 2871 (w), 1593 (w), 1537 (w),
489 (w), 1453 (w), 1408 (w), 1314 (m), 1294 (m), 1191 (s), 1086 (s), 1072
s), 1012 (w), 931 (s), 834 (w), 795 (m), 738 (m), 676 (w), 640 (w), 603 (w),
2 5 3
F )
1
iodine (1.41 g, 5.56 mmol) in n-pentane (5 mL). After stirring for 1 h at
room temperature the violet solution was cooled to -40 °C and all volatile
compounds were removed. The residue was stirred over a few drops of
mercury until the violet color vanished. The product was condensed of and
last residues of n-pentane were removed at -40 °C. The product was
obtained as a colorless liquid (2.93 g, 4.86 mmol, 93 %). Vapor pressure
(
-
1
5
87 (w), 536 (w), 491 (w), 430 (w) cm .
2 5 3
Reaction of HSn(C F ) with 1,6-diiodo-, 1,6-dibromo-, and 1,6-
dichlorohexane: 1,6-Diiodohexane (0.115 g, 0.34 mmol), dibromohexane
1
3
19
(
22 °C): 7 mbar; C{ F} NMR ([D
2
]dichloromethane, 298 K): d=121.6 (s,
(0.084 g, 0.34 mmol) and 1,6-dichlorohexane (0.052 g, 0.34 mmol) were
1
2
J(C,Sn)=622/651 Hz; CF
2
), 118.8 ppm (s, J(C,Sn)=100/105 Hz; CF
3
);
combined in chloroform (10 mL) and HSn(C
condensed onto the solution. The solution was cooled to -80 °C and was
allowed to reach room temperature overnight to give colorless
suspension. The crude product solution was investigated by NMR
spectroscopy to obtain the resonances for ISn(C , 1,6-dibromo-, 1,6-
dichlorohexane and n-hexane. H NMR (chloroform/[D ]acetone, 298 K):
), 3.37 (t, J(H,H)=6.7 Hz, 4H; Br-
), 1.74 (m, 4H; Br-CH -CH ), 1.43 (m, 4H;
), 1.43 (m, 4H; Br-CH -CH -CH ), 1.22 (m, 6.6H; CH (n-
hexane)), 0.83 ppm (t, J(H,H)=6.9 Hz, 4.8H; CH (n-hexane)); F NMR
]acetone, 298 K): d=-81.3 (s, 9F; CF ), -108.4 ppm (s,
). After filtration all volatile compounds were
2 5 3
F ) (0.45 g, 0.94 mmol) was
1
9
F NMR ([D
2
2
]dichloromethane, 298 K): d=-81.8 (s, 9F; CF ), -108.8 ppm
3
119
1
(
s, J(F,Sn)=402/422 Hz, 6F; CF
2
); Sn{ H} NMR ([D
2
]dichloromethane,
a
2
2
98 K): d=-322.6 ppm (sept, J(Sn,F)=421 Hz); MS (EI, 70 eV, pos.) {m/z
+
+
(
%) [assignment]}: 484.8 (45) [ISn(C
2
F
5
)
2
] , 384.8 (100) [ISnF(C
2
F
5
)] ,
2 5 3
F )
+
+
+
∙+
] ,
1
2
6
9
84.8 (20) [ISnF
2
] , 246.8 (67) [SnI] , 138.9 (61) [SnF] , 100.0 (39) [C
2
F
4
6
+
~
3
3
9.0 (21) [CF ] ; IR (gas phase): n=1319 (s), 1297 (m), 1226 (s), 1118 (s),
37 (m), 742 (m), 606 (w), 536 (w) cm .
3
d=3.50 (t, J(H,H)=6.7 Hz, 4H; Cl-CH
CH ), 1.83 (m, 4H; Cl-CH -CH
Cl-CH -CH -CH
2
-
1
2
2
2
2
2
2
2
2
2
2
2
2
3
19
Synthesis of iodotris(pentafluoroethyl)-1,10-phenanthrolinetin(IV): A
sample of ISn(C (0.54 g, 0.90 mmol) was condensed onto a solution
3
(
2
chloroform/[D
6
3
2 5 3
F )
J(F,Sn)=403/423 Hz, 6F; CF
2
of 1,10-phenanthroline (0.09 g, 0.5 mmol) in dichloromethane (5 mL). The
solution was stirred for 1 h at room temperature while a colorless solid
precipitated. Removing all volatile compounds under reduced pressure
furnished the product as an off white solid (0.42 g, 0.5 mmol, 100 %).
-
3
removed in high vacuum (1x10 mbar) to obtain a 1:1 mixture of 1,6-
1
dibromo- and 1,6-dichlorohexane (0.13 g, 96 %). H NMR ([D]chloroform,
3
3
2
4
1
98 K): d=3.56 (t, J(H,H)=6.7 Hz, 4H; Cl-CH
H; Br-CH ), 1.89 (m, 4H; Cl-CH -CH ), 1.81 (m, 4H; Br-CH
.49 ppm (m, 8H; X-CH -CH ).
2
), 3.43 (t, J(H,H)=6.7 Hz,
Crystals suitable for X-ray diffraction were grown from a dichloromethane
2
2
2
2
-CH ),
2
1
solution at -25 °C. M.p. (decomp.): 205 °C; H NMR ([D
3
]acetonitrile,
2
2
3
3
2
9
98 K): d=9.98/9.44 (2 d, J(H,H)=5.1 Hz, J(H,H)=5.1 Hz, 2H; H2/H9),
3
4
3
.07/9.03 (2 dd, J(H,H)=8.3 Hz, J(H,H)=1.5 Hz, J(H,H)=8.3 Hz,
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Chemistry - A European Journal
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Reaction of HSn(C
2
F
5
)
3
with 6-bromo-1-hexene in n-pentane: A sample
Reaction of HSn(C
2
F
5
)
3
with cyclohexyl bromide and ethyl acrylate: In
of HSn(C (1.14 g, 2.39 mmol) was condensed onto a solution of 6-
2
F
5
)
3
2 5 3
a Young valve NMR tube HSn(C F ) (0.1 g, 0.21 mmol) was combined
bromo-1-hexene (0.41 g, 2.51 mmol) in n-pentane (10 mL). The solution
with ethyl acrylate (0.02 g, 0.20 mmol) and cyclohexyl bromide (0.02,
0.12 mmol) in [D]chloroform (1 mL). The reaction was completed after
minutes. The raw product mixture was investigated by NMR spectroscopy
to obtain the resonances for cyclohexyl bromide and ethyl 3-
was stirred overnight at room temperature. All volatile compounds were
-
3
removed in high vacuum (10 mbar) and investigated by NMR
1
2 5 3
spectroscopy to obtain the resonances for BrSn(C F ) and 1-hexene. H
3
1
NMR (n-pentane/[D
6
]acetone, 298 K): d=6.36 (d, d, t, J(H,H)=17.0 Hz,
[tris(pentafluoroethyl)stannyl]propionate. H NMR ([D]chloroform, 298 K):
3
2
3
3
3
3
J(H,H)=10.3 Hz, J(H,H)=6.7 Hz, 1H; =CH), 5.56 (d, d, t, J(H,H)=17.0 Hz,
d=4.36 (q, J(H,H)=7.1 Hz, 2H; OCH
2
), 4.22 (m, 0.6H; CHBr); 2.81 (t,
CH ), 2.18 (m, 1.1H, Cy-Br),
1.9-1.3 (m, Cy-Br), 1.80 (t, J(H,H)=7.7 Hz; Sn-CH ), 1.34 ppm (t,
); F NMR ([D]chloroform, 298 K): d=-82.9 (s, 9F;
4
3
3
J(H,H)=2.1 Hz, J(H,H)=2.1 Hz, 1H; CH
2
=CH(trans)), 5.49 (d, d, t,
J(H,H)=7.6 Hz, J(H,Sn)=104 Hz, 2H; Sn-CH
2
2
2
4
3
J(H,H)=10.1 Hz, J(H,H)=2.1 Hz, J(H,H)=1.4 Hz, 1H; CH
2
=CH(cis)),
=CH-CH
2
3
3
3
19
2
.66 ppm (d, t, m, J(H,H)=7 Hz, J(H,H)=7 Hz, 2H; CH
2
9
2
)
J(H,H)=7.1 Hz; CH
3
1
2
(
additional signals were covered by the solvent resonances); F NMR (n-
pentane/[D ]acetone, 298 K): d=-82.3 (s, 9F; CF ), -108.8 ppm (s,
J(F,Sn)=427/447 Hz, 6F; CF ). In order to clear the question if
methylcyclopentane, as the product of a C-C coupling reaction is formed
the reaction was repeated in n-decane. Thus, HSn(C (0.75 g,
.57 mmol) was condensed onto a solution of 6-bromo-1-hexene (0.29 g,
.78 mmol) in n-decane (10 mL). The reaction was completed after 1 h at
3 2
CF ), -114.4 ppm (s, J(F,Sn)=290/300 Hz, 6F; CF ).
6
3
2
2
Reaction of HSn(C
2 5 3 2 5 3
F ) with allyl bromide: A sample of HSn(C F )
(
0.32 g, 0.67 mmol) and allyl bromide (0.14 g, 1.2 mmol) were condensed
2 5 3
F )
onto [D]chloroform (1 mL) in a Young-valve NMR tube. After 12 h the raw
1
1
product solution was investigated by NMR spectroscopy to obtain the
1
resonances for allyl bromide, BrSn(C
2
F
5
)
3
and propene.
H NMR
3
3
room temperature. All volatile compounds were removed at high vacuum
(
3
[D]chloroform, 298 K): d=6.05 (d, d, t, J(H,H)=17.0 Hz, J(H,H)=9.7 Hz,
-
3
(
10 mbar) and investigated by NMR spectroscopy to obtain the
resonances for BrSn(C , (C SnSn(C , 6-bromo-1-hexene and
-hexene. Even though the fact that residues of n-decane prevent a
J(H,H)=7.2 Hz, 2H; =CH(allyl bromide)), 5.84 (m, 1H; =CH(propene)),
3
2
F
5
)
3
2
F
5
)
3
2
F
5
)
3
5
.33 (d, m, J(H,H)=16.7 Hz, 4H; CH
2
=CH(trans)(allyl bromide)), 5.16 (d,
3
1
m, J(H,H)=10.2 Hz, 4H; CH
2
CH=(cis)(allyl bromide)), 5.04 (d, d, q,
1
13
meaningful H NMR spectrum the C spectrum show no resonances for
3
2
4
J(H,H)=17.0 Hz,
J(H,H)=1.9 Hz
4.95 (d,
J(H,H)=1.9 Hz,
3
1H;
1H;
Br),
1
9
methylcyclohexane.
BrSn(CF CF ), -82.4 (s, 0.7F; Sn
J(F,Sn)=30 Hz, 0.7F; Sn (CF CF
); C{ H} NMR ([D]chloroform, 298 K): d=139.2 (s;
(1-hexene)), 138.1 (s; CH=CH (6-bromo-1-hexene)), 114.9 (s;
(6-bromo-1-hexene)), 114.0 (s; CH=CH (1-hexene)), 33.54 (s;
(1-hexene)), 32.8 (s; CH-CH (6-bromo-1-
(6-bromo-1-hexene)), 31.1 (s; CH (1-hexene)), 27.3
(6-bromo-1-hexene)), 22.2 (CH (1-hexene)), 13.8 ppm (s, CH ).
F NMR ([D]chloroform, 298 K) d=-81.6 (s, 9F;
CH
CH
2
=CH(cis)(propene)),
m,
3
J(H,H)=10.0 Hz,
2
2
3
)
3
2
(CF
2 3 6
CF ) ), -104.1 (s, J(F,Sn)=378 Hz,
=CH(cis)(propene)), 3.95 (d, m, J(H,H)=7.3 Hz, 4H; CH
2
2
3
2
)
6
), 109.8 ppm (s, J(F,Sn)=438/458 Hz,
3
4
4
2
2
3
1
.73 ppm (d, d, d, J(H,H)=6.4 Hz, J(H,H)=1.5 Hz, J(H,H)=1.5 Hz, 3H,
1
3
1
1
9
6
2 3 3
.7F, BrSn(CF CF )
3 3
CH (propene)); F NMR ([D]chloroform, 298 K): d=-82.1 (s, 9F; CF ), -
2
CH=CH
CH=CH
2
2
2
1
2
08.9 ppm (s, J(F,Sn)=429/448 Hz, 6F; CF ).
2
CH
hexene)), 32.2 (s; CH
s; CH
2
-Br), 33.48 (s; CH-CH
2
2
2
2
(
2
2
3
Table 1. Structure refinement data of HSn(C
HSn(C
2
F
5
)
3
, [SnI(C
2
F
5
)
3
(phen)], MePh
2
CSn(C
(phen)]
Cl
Crystallographic Section
ClF15IN Sn
2
F
5
)
3
, PhC
2
H
2
Sn(C
2 5 3
F ) .
[
SnI(C
2 5 3
F )
2
F
5
)
3
MePh CSn(C
2
2
F
5
)
3
2 2 2 5 3
PhC H Sn(C F )
∙
1/2(CH
2
2
)
empirical formula
a / pm
b / pm
c / pm
C
6
HF15Sn
C
18.5
H
9
2
C
20
H
13
F
15Sn
14 7
C H F15Sn
840.82(6)
1141.98(7)
1280.19(7)
90
1718.49(2)
958.054(8)
2977.67(4)
90
779.793(7)
943.485(8)
1690.726(18)
1350.688(12)
1660.188(18)
90
1589.499(13)
104.0761(7)
95.9006(7)
99.6486(7)
1105.596(17)
2
a / °
b / °
94.877(5)
90
100.7683(11)
90
109.9259(12)
90
g / °
6
3
V / 10 ∙ pm
1224.79(13)
4
4816.12(9)
8
3564.31(7)
8
Z
-
3
ρ
calc / mg∙mm
2.586
2.276
1.974
2.158
crystal system
space group
monoclinic
P21/n
monoclinic
I2/a
triclinic
monoclinic
I2/a
P-1
shape / color
colorless in capillary
0.30 x 0.25 x 0.25
colorless fragment
0.32 x 0.25 x 0.10
colorless in capillary
0.60 x 0.16 x 0.15
colorless in capillary
0.64 x 0.19 x 0.16
-
3
crystal size / mm
Data Collection
diffractometer
Nonius Kappa CCD
Agilent Supernova
2.583
Agilent Supernova
Agilent Supernova
1.582
1
μ / mm
-
2.270
888
1.288
636
F(000)
3112
2208
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Chemistry - A European Journal
10.1002/chem.201705068
Full Paper
2
θ range for data
6
.0 to 60.1
6.4 to 60.1
4.5 to 64.1
4.0 to 60.1
collection / °
-
11 ≤ h< ≤ 11
-24 ≤ h ≤ 24
-13 ≤ k ≤ 13
-41 ≤ l ≤ 41
-11 ≤ h ≤ 11
-14 ≤ k ≤ 13
-23 ≤ l ≤ 23
-23 ≤ h ≤ 23
-19 ≤ k ≤ 19
-23 ≤ l ≤ 23
index ranges
-16 ≤ k ≤ 16
-
18 ≤ l ≤ 18
45288
reflections collected
independent reflections
R(int)
319159
7031
66404
7318
60510
5226
3559
0.0493
0.0503
0.0374
0.0381
data/restraints/paramete
rs
3
559/0/205
1.137
7031/0/358
7318/0/377
5226/0/299
2
goodness-of-fit on F
1.097
1.073
1.057
R
1
/ wR
/ wR
2
[I≤2σ(I)]
0.0227/ 0.0499
0.0276/0.0524
0.67/-1.00
0.0167/0.0425
0.0174/0.0428
0.77/-0.65
0.0187/0.0477
0.0219/0.0481
0.53/-0.36
0.0171/0.0418
0.0193/0.0426
0.64/-0.28
R
1
2
(all data)
-
3
Δρmax/min / e Å
CCDC number
1001350
1565485
1565486
1565487
3
96; c) M. Henrich, A. Marhold, A. Kolomeitsev, A. Kadyrov, G.-V.
Röschenthaler, J. Barten, DE 101 28 703 1, 2001; d) M. H.
A
Acknowledgements
Königsmann, PhD thesis, Universität Bremen, Bremen, 2005; e) 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,
11640–11644; Angew. Chem. 2014, 126, 11824–11828.
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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[
[
3
Keywords: pentafluoroethyl • stannane • electron-deficient •
hydrostannylation• dehalogenation
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Chemistry - A European Journal
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
A versatile two-step synthesis for
tris(pentafluoroethyl)stannane,
Markus Wiesemann, Mark Niemann,
Johannes Klösener, Beate Neumann,
Hans-Georg Stammler and Berthold
Hoge*
2 5 3
HSn(C F ) , as a rare example of an
electron deficient stannane is
presented. The utility of this stannane
was illustrated in hydrostannylations
of alkenes and alkynes as well as in
dehalogenation reactions in the
absence of activators. In the latter
case the formation of volatile tin-
Page No. – Page No.
Tris(pentafluoroethyl)stannane: Tin
Hydride Chemistry with an Electron-
deficient Stannane
containing by-products, XSn(C
2 5 3
F )
(
X = I, Br), allows a facile separation.
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