Activation of SF6 at Platinum Complexes: Formation of SF3 Derivatives and Their Application in Deoxyfluorination Reactions

Article abstract of DOI:10.1002/anie.201612417

The activation of SF₆ at [Pt(PR₃)₂] R=Cy, iPr complexes in the presence of PR₃ led selectively and in an unprecedented reaction route to the generation of the SF₃ complexes trans-[Pt(F)(SF₃)(PR₃)₂]. These can also be synthesized from SF₄ and the SF₂ derivative trans-[Pt(F)(SF₂)(PCy₃)₂][BF₄] was characterized by X-ray crystallography. trans-[Pt(F)(SF₃)(PR₃)₂] complexes are useful tools for deoxyfluorination reactions and novel fluorido complexes bearing a SOF ligand are formed. Based on these studies a process for the deoxyfluorination of ketones was developed with SF₆ as fluorinating agent.

Full text of DOI:10.1002/anie.201612417

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201612417
German Edition: DOI: 10.1002/ange.201612417
Fluorination
Activation of SF6 at Platinum Complexes: Formation of SF3 Derivatives
and their Application in Deoxyfluorination Reactions
Claudia Berg, Thomas Braun,* Mike Ahrens, Philipp Wittwer, and Roy Herrmann
Abstract: The activation of SF6 at [Pt(PR3)2] R = Cy, iPr
complexes in the presence of PR3 led selectively and in an
unprecedented reaction route to the generation of the SF3
complexes trans-[Pt(F)(SF3)(PR3)2]. These can also be syn-
thesized from SF4 and the SF2 derivative trans-[Pt(F)(SF2)-
(PCy3)2][BF4] was characterized by X-ray crystallography.
trans-[Pt(F)(SF3)(PR3)2] complexes are useful tools for deox-
yfluorination reactions and novel fluorido complexes bearing
a SOF ligand are formed. Based on these studies a process for
the deoxyfluorination of ketones was developed with SF6 as
fluorinating agent.
electron-transfer to SF6 occurs to generate a radical anion to
yield via unknown steps a (RO)SFx intermediate, which
À
further reacts by C O cleavage and fluorination. Another
report, which is covered by a patent,[10a] deals with the
reduction of SF6 to produce the SF5À anion.[10] This anion was
shown to be a bad fluorinating agent.
Herein we present the selective and remarkable activation
of SF6 at [Pt(PR3)2] (1: R = Cy, 3: R = iPr). In the presence of
additional phosphine no depletion was observed, but the
complexes trans-[Pt(F)(SF3)(PR3)2] (2: R = Cy, 4: R = iPr)
are generated which contain a metal-bound SF3 building
block. These complexes can be used for fluorination reactions
and are hence intermediates in deoxyfluorination reactions of
ketones with SF6 as fluorinating agent.
The development of new routes to access organic building
blocks by selective fluorination is of enormous importance for
the construction of new materials and bioactive compounds.[1]
Among various fluorination reagents deoxyfluorinating
derivatives are widely used to convert for instance alcohols
into alkyl fluorides, ketones or aldehydes into gem-di-
fluoroalkanes as well as carboxylic groups into trifluoro-
methyl groups.[1b,2] Common reagents include SF4 and some
derivatives of it, such as Fluolead, DAST or Deoxo-Fluor
among others. However, they often have to be generated from
SF4 or via oxidative fluorination of sulfides.[3] An interesting
alternative reagent for deoxyfluorination comprises 2-pyridi-
nesulfonylfluorid, which can be prepared from potassium
bifluoride.[4] A very exciting route to prepare sulfur-contain-
ing fluorinating agents involves SF6 as active agent, but
reported attempts are scarce.[5] This is consistent with the fact
that SF6 is an extremely inert gas, which is used as dielectric in
high-voltage circuit breakers.[6] Generally, SF6 can be acti-
vated and depleted by reduction. This activation was achieved
at low-valent Ti, V, Cr, and Zr complexes as well as at Fe and
at reduced Ni complexes.[7] We previously described the
selective degradation of SF6 at a binuclear rhodium complex
as well as the catalytic transformation of SF6 into fluorosilanes
and phosphinesulfides with [Rh(H)(PEt3)4] as catalytic pre-
cursor.[8] A breakthrough for using SF6 in organic synthesis
was very recently reported by McTeague and Jamison. They
developed an iridium-based photoredox catalytic process
leading to a deoxyfluorination of allylic alcohols to form
fluorinated olefins.[9] It is speculated that in an initial step an
Treatment of [Pt(PCy3)2] (1) with SF6 in the presence of
PCy3 led after 16 h at 608C to the SF3 fluorido complex trans-
[Pt(F)(SF3)(PCy3)2] (2) and F2PCy3 (Scheme 1).[11] The reac-
Scheme 1. Formation and reactivity of the SF3 complexes 2 and 4.
tion does not take place if no additional PCy3 is present.
However, an independent experiment showed that PCy3 does
not react with SF6. A similar activation reaction was found at
[Pt(PiPr3)2] (3)/PiPr3 to yield trans-[Pt(F)(SF3)(PiPr3)2] (4)
(Scheme 1). Alternatively, the complexes 2 and 4 can be
synthesized by treatment of a suspension of either [Pt(PCy3)2]
(1) or [Pt(PiPr3)2] (3) in n-hexane with SF4. The conversions
were complete within minutes at room temperature
(Scheme 1). Comparable insertion reactions at [Pt(PCy3)2]
(1) into element–fluorine bonds in BF3 or PF5 were described
by Finze and Braunschweig et al.[12]
[*] C. Berg, Prof. Dr. T. Braun, Dr. M. Ahrens, P. Wittwer, Dr. R. Herrmann
Department of Chemistry
Humboldt-Universitꢀt zu Berlin
Brook-Taylor-Strasse 2, 12489 Berlin (Germany)
E-mail: thomas.braun@chemie.hu-berlin.de
The 19F NMR spectrum of 2 shows two resonance signals
for the SF3 ligand and one for the fluorido ligand bound at the
metal center. A doublet of doublet like pattern at d =
À326.3 ppm with coupling constants of 2JF,P = 17 Hz and
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
http://dx.doi.org/10.1002/anie.201612417.
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2JF,P = 21 Hz with 195Pt satellites reveals the presence of the
metal-bound fluorido ligand.[13] Two signals with 195Pt satel-
lites at d = 58.0 ppm and d = À71.3 ppm which integrate 2:1
correspond to the sulfur bound fluorides. The coupling
between the two sets of fluorine atoms is 63 Hz. Note that
the complexes [Ir(CO)(X)(F)(PEt3)2(SF3)] (X = Br, Cl, I),
which were synthesized from SF4 exhibit a nonequivalence of
all three fluorine atoms bound at the SF3 unit.[14] The 31P{1H}
NMR spectrum (242.9 MHz) of 2 at 263 K exhibits two
resonance signals of higher order for the two nonequivalent
phosphorous atoms at d = 31.2 ppm and d = 22.8 ppm. To
determine the coupling constants the 31P{1H} NMR spectrum
was simulated (Supporting Information). The pattern reveals
a phosphorous–phosphorous coupling constant of 334 Hz,
which is typical for phosphines in a mutually trans position.[15]
Additional splittings are due to couplings to the four fluorine
atoms. The values for the phosphorus-platinum coupling
constants (1JPa,Pt = 2745 Hz, 1JPb,Pt = 2614 Hz) are character-
istic for a PtII species.[13a,b,e,j–l,16] Variable temperature 31P{1H}
NMR spectroscopy reveals a fluxional structure rendering the
phosphorous atoms to be equivalent at 348 K (121.5 MHz, see
Supporting Information). Because the NMR spectroscopic
data of complex 4 are very similar to those of 2, no further
discussion is given (see Supporting Information). It is likely
that the non-equivalence of the two phosphorus nuclei arises
from a trigonal bipyramidal arrangement of the fluorine
atoms, the metal center as well as a lone electron pair at
sulfur. DFT calculations on the molecular structure of 2
confirm such geometry of the SF3 group and the HOMOÀ1 is
located at the sulfur atom (Figure 1, Supporting Information).
This gives possibly a SF5 fluorido platinum complex, but SF5
complexes have so far been elusive.[20] However, intra- or
intermolecular fluoride abstraction from the SF5 ligand would
À
finally lead to 2 and 4. Note that phosphine assisted C F bond
activations which involve an addition of the carbon-fluorine
bond across a metal–phosphorus bond have been repor-
ted.[13c,k,15,21] Though, when 2 was generated in the presence of
PiPr3 instead of PCy3, the generation of F2PiPr3 was observed.
The identity of 2 was further confirmed by the generation
of trans-[Pt(F)(SF2)(PCy3)2][BF4] (5) and trans-[Pt(F)(SF2)-
(PiPr3)2][BF4] (6) on treatment of the SF3 complexes with
a solution of BF3 in Et2O (Scheme 1). The iridium complex
[Ir(CO)(Cl)(F)(PEt3)2(SF3)] reacts in a similar way to give
[Ir(CO)(Cl)(F)(PEt3)2(SF2)] [BF4].[14]
The 19F NMR spectrum of 5 shows signals at d =
3
À35.7 ppm a triplet with a coupling constant of JF,P = 21 Hz
with 195Pt satellites, which corresponds to the SF2 unit. Again
a triplet at d = À252.7 ppm (2JF,P = 24 Hz) with 195Pt satellites
is characteristic for the fluorido ligand bound at a metal
center.[12] The 31P{1H} NMR spectrum of 5 reveals a resonance
at d = 42.7 ppm as a doublet of triplet pattern (3JF,P = 21 Hz;
2JF,P = 24 Hz). The value for the phosphorus-platinum cou-
pling constant (1JP, Pt = 2071 Hz) is characteristic for a PtII
species.[13a,b,e,j–l,16] The data of 6 are comparable to these of 5.
The structure of 5 in the solid state was determined by X-ray
crystallography (Figure 2). Complex 5 exhibits an approx-
imately square-planar coordination sphere at the platinum
À
À
center. The S1 F2 and S1 F3 [1.5814(17); 1.5765(16)] bond
À
lengths are comparable to S F bonds in deoxyfluorination
agents such as morpholinesulfurtrifluoride (MOST) and the
bis(diethylamino)difluorosulfonium cation.[22] There are short
contacts of S1-F’1 2.8959(18) and 2.9839(19) S1-F’3 between
the BF4À ion and the metal bound sulfur atom.
Furthermore, the reactivity of the complexes 2 and 4 were
tested towards organic substrates. Thus, a reaction of 2 with
ethanol led to the generation of trans-[Pt(F)(SOF)(PCy3)2]
Figure 1. DFT-optimized structure of complex 2.
This observation is consistent with calculations by B. King
et al. for [Ir(SF3)(CO)3], for which the SF3 ligand is consid-
ered to be a one-electron donor, that is, an anionic two-
electron donor.[17] However, it is in contrast to the suggested
electronic structure of [Pt(Cp)(SF3)] (Cp = cyclopentadienyl),
for which the SF3 ligand is considered to be a three electron
donor resulting in a tetrahedral environment at sulfur.
Mechanistically, we presume that the SF6 activation is
initiated by an electron-transfer step from the metal to the SF6
molecule.[7–10,18] This might be facilitated by a precoordination
of the fluorinated substrate at the platinum center followed by
an inner-sphere mechanism to yield SF5À and a fluoride ion.[10]
Figure 2. ORTEP diagram of 5·toluene. Ellipsoids are set at 50%
probability. Hydrogen atoms and a toluene molecule are omitted for
clarity. Selected bond lengths [ꢁ] and angles [8]: Pt1–S1 2.1108(6), Pt1–
F1 1.9810(13), Pt1–P1 2.3720(7), Pt1–P2 2.3731(6), S1–F2 1.5814(17),
S1–F3 1.5765(16), B1–F’1 1.386(4); F1-Pt1-S1 174.52(4), F1-Pt1-P1
85.34(4).
Comparable mechanistic steps have been suggested for
[1a,f,19]
À
transition-metal mediated C F activation reactions.
2
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(7) as well as of EtFand HF by deoxyfluorination (Scheme 2).
deoxyfluorination of the benzophenones with SF6 as fluori-
To our knowledge 7 represents a unique example of
a transition metal SOF complex. The 19F NMR spectrum of
7 exhibits at d = À5.0 ppm a triplet with a coupling constant of
nating agent was also tested. On using 20 mol% of 2 44%
conversion of benzophenone to the corresponding deoxy-
fluorinated product was observed according to the NMR
spectra after 5 days at 808C. Though, slightly more than two
equivalents of the fluorinated product are generated based on
one equivalent SF6.
In conclusion, we have developed transition-metal medi-
ated fluorination reactions with SF6 as the fluorinating agent.
The unprecedented conversions reveal an initial activation at
Pt0 complexes to yield the SF3 complexes trans-[Pt(F)(SF3)-
(PR3)2]. Remarkably, the SF6 molecule is not depleted, but
transformed into a SF3 group and a metal fluoride ligand. The
generation of a stable sulfur fluoride species in a lower
oxidation state from SF6 is extraordinary and the conversions
are in strong contrast to other reactions at transition-metal
complexes, which result in a depletion of SF6.[7,8] Note that
even decomposition reactions of SF5 groups bound at organic
molecules are rare.[23] The SF3 complexes can then be applied
in deoxyfluorination reactions of ketones and all four fluorine
atoms are transferred to the organic substrate. Future studies
aim for catalytic deoxyfluorination on using the greenhouse
gas SF6 as fluorinating agent.
Scheme 2. Reactivity of 2 and 4 towards organic substrates.
3JF,P = 12 Hz with 195Pt satellites and a triplet at d = À285 ppm
(2JF,P = 15 Hz) with 195Pt satellites for the fluorido ligand.[13]
The 31P{1H} NMR spectrum of 7 depicts a doublet of doublet
with 3JP,SOF = 12 Hz and 2JP, PtF = 15 Hz with 195Pt satellites
(1JP, Pt = 2650 Hz). The molecular structure of 7 was also
determined by X-ray crystallography. Although the structure
reveals a positional disorder of the oxygen and fluorine atoms
about the sulfur atom, and the oxygen and fluorine atoms
were only refined isotropically, the data are consistent with
the proposed structure (Figure 3, and Supporting Informa-
tion).
Acknowledgements
We acknowledge the DFG (Deutsche Forschungsgemein-
schaft) for financial support. We also thank the Solvay Fluor
GmbH for a gift of SF6.
Conflict of interest
The authors declare no conflict of interest.
Complex 2 can also be applied for the fluorination of non-
enolizable ketones. Thus, a reaction with two equivalents of
benzophenone or 3-(trifluoromethyl)benzophenone led to
À
Keywords: fluorination · fluorine · platinum · S F activation ·
sulfurhexafluoride
the
regeneration
of
1
and
produced
bis-
(phenyl)difluoromethane derivativesand SO2 (Scheme 2).
The SO2 was identified by GC/MS. Note that a catalytic
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4
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These are not the final page numbers!

Angewandte
Communications
Chemie
Int. Ed. Engl.Angew. Chem. Int. Ed. 1978, 17, 516 – 518; Angew.
Chem. 1978, 90, 547 – 549; h) P. Kirsch, M. Bremer, M. Heck-
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Manuscript received: December 22, 2016
Final Article published: && &&, &&&&
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Fluorination
Special eFFects: The activation of SF6 at
Pt complexes yields SF3 fluorido com-
plexes which can be used for the fluori-
nation of ketones.
C. Berg, T. Braun,* M. Ahrens, P. Wittwer,
R. Herrmann
&&&& — &&&&
Activation of SF6 at Platinum Complexes:
Formation of SF3 Derivatives and their
Application in Deoxyfluorination
Reactions
6
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ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
These are not the final page numbers!