No Fear of Perfluorinated Peroxides: Syntheses and Solid-State Structures of Surprisingly Inert Perfluoroalkyl Peroxides

Article abstract of DOI:10.1002/anie.201814417

We report on the solid-state structures of bis(nonafluoro-tert-butyl) peroxide [(F₃C)₃CO]₂ and bis(undecafluoro-2-methyl-2-butyl) peroxide [(C₂F₅)(F₃C)₂CO]₂. These peroxides were prepared from the corresponding hypofluorites and fluorinated silver wool. The solid-state structures obtained after in situ crystallisation show unusual COOC dihedral angles of 180°, as well as elongated O?O bonds because of the bulky perfluorinated alkyl groups. The perfluorinated alkyl peroxides are insensitive to both impact (>40 J) and friction (>360 N), and resistant towards mineral acids (HX; X=F, Cl, Br) and elemental halogens (X₂). Ferrocene is oxidized by [(F₃C)₃CO]₂ to [Fe^IIICp₂][OC(CF₃)₃].

Full text of DOI:10.1002/anie.201814417

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Accepted Article
Title: No fear for Perfluorinated Peroxides: Syntheses and Solid State
Structures of Surprisingly inert Perfluoroalkyl Peroxides
Authors: Sebastian Hasenstab-Riedel, Jan Hendrick Nissen, Tony
Stüker, Simon Steinhauer, Helmut Beckers, and Thomas
Drews
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201814417
Angew. Chem. 10.1002/ange.201814417
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Angewandte Chemie International Edition
10.1002/anie.201814417
COMMUNICATION
No fear for Perfluorinated Peroxides: Syntheses and Solid State
Structures of Surprisingly inert Perfluoroalkyl Peroxides
a
a
a
a
a
Jan H. Nissen , Tony Stüker , Thomas Drews , Simon Steinhauer , Helmut Beckers , Sebastian
Riedela*
Abstract: We report on the solid state structures of bis(nonafluoro-
tert-butyl) peroxide [(F C) CO] and bis(undecafluoro-2-methyl-2-
butyl) peroxide [(C )(F C) CO] . These peroxides are prepared from
synthesis by treatment of carbonyl fluoride with elemental fluorine
was reported in 1933 by Swarts[8] and later by Cady et al.[9]
3
3
2
2
F
5
3
2
2
Compared to (H
rather stable (up to 200 °C). This very different reaction behavior
of the most simple dialkyl peroxides, (H CO) vs. (F CO) , cannot
3 2
CO) it is amazingly resistant and thermally
[
7]
the corresponding hypofluorites with fluorinated silver wool. Their
solid state structures obtained by in situ crystallization show unusual
COOC dihedral angles of 180°, as well as elongated O–O bonds as a
result of the bulky perfluorinated alkyl groups. The perfluorinated alkyl
3
2
3
2
solely be attributed to their different bond dissociation energies.
The O–O bond energy of dialkyl peroxides ROOR is about
peroxides are insensitive to both, impact (> 40 J) and friction (> 360 N), 1604 kJ mol–1 and almost independent of the nature of R,
[7, 10,11]
and resistant towards mineral acids (HX, X = F, Cl, Br) and elemental
while that of F
3
CO–OCF
3
was estimated in two independent
III
[7]
–1 [11]
halogens (X
OC(CF ].
2
). Ferrocene is oxidized by [(F
3 3
C) CO]
2
to [Fe Cp
2
]
studies to 1932 and 1992 kJ mol . The main difference
between the decomposition behavior of the two peroxides is due
to secondary reactions of the initially formed alkoxy radicals, RO•.
[
3 3
)
These are slow and endothermic with respect to (F
but very fast and strongly exothermic for the dimethyl analogue
CO)
(eq. 2).[7]
3 2
CO) (eq. 1),
The introduction of fluorine into organic compounds often
significantly modifies their physicochemical properties and their
(
H
3
2
F
F
reactivity. Perfluorinated alkyl peroxides R OOR (1) are among
those organic compounds about which our knowledge is so far
only rather scarce. This is surprising since they have been
claimed in a few previous studies as synthetically valuable
sources of fluorinated alkoxy radicals,[1][2] and their non-
2
2
F
H
3
CO•  F
CO•  H
3
COF + F
2
CO
CO
(1)
(2)
3
3
COH + H
2
More recently the O–O bond dissociation energy of peroxides has
been taken up again in a broader scope by several computational
studies.[10][11][12]
[
3]
fluorinated counterparts are known for more than a century. In
3]
1
858 Brodie discovered the first organic peroxides,[ which
nowadays are widely used in chemical synthesis and industrial
processes, such as in oxidation and polymerisation reactions.[4][5]
They also play an important role in atmospheric chemistry, e.g. in
Apart from (F
to our knowledge has been studied so far is the bis(nonafluoro-
tert-butyl) peroxide, [(F C) CO] (1a). It was first obtained among
other by-products by Gould et al. from the reaction of (F C) COH
with the very strong oxidizer chlorine trifluoride (ClF ) in a high-
3 2
CO) , the only perfluorinated alkyl peroxide which
the ozone depletion.[6] The prototype dimethyl peroxide, (H
bp.: 14 °C), is formed in the stratosphere by oxidation of
CO)
2
3
3
3
2
(
3
3
methane.[ The versatile use of such peroxides as catalyst and
activators is based on their ability to break down in a clean way to
form alkoxy radicals that initiate chain reactions.[3][4] The cleavage
of the peroxy bond in pure alkyl peroxides, which requires only a
comparatively low thermal energy and can also easily be initiated
catalytically, often cause a very exothermic decomposition
reaction, which in may lead to an explosion or even detonation.[5]
Liquid dimethyl peroxide is reported to be shock-sensitive and its
vapour is subject to explosive decomposition.[7] However, as was
mentioned 60 years ago by Rieche,[3] the more a peroxide bond
is bound to larger organic groups, the more harmless it will be,
and when a large and a small organic group are bound to a
peroxide group, the larger one determines its temperament.
We are interested in the properties of perfluorinated alkyl
peroxides. So far the most investigated perfluorinated alkyl
7]
3
pressure stainless-steal reactor,[13] and it was later shown, that
also the low-temperature photolysis (200 W Hg-lamp in a quartz
reactor) of mixtures of perfluoro tert-butyl hypofluorite, (F
3
C) COF
3
(
2a) in the presence of fluorine acceptors such as
[14]
,[1] yield the
2 4
or tetrafluorohydrazine, N F
perfluorocycloolefins
peroxide 1a. The 19F NMR spectrum ( = –70.0 ppm relative to
internal CFCl
3
) and the four strongest absorptions in the mid-IR
[13]
spectrum of 1a have been reported. Its thermal decomposition
3 2 2 6
was investigated to produce exclusively (F C) CO and C F with
an activation energy of 1484[15] kJ mol . Surprisingly, only
–1 [1]
photochemical reaction of 1a with perfluorocyclo olefins have
[1]
been studied so far. These earlier studies prove that 1a can be
used to transfer perfluoro tert-butylalkoxy groups to organic
olefins.
3 2
peroxide is bis(trifluoromethyl) peroxide, (F CO) (bp.: –37 °C). Its
Apart from the sparely investigated photochemistry the reactivity
and structural properties of such bulky perfluorinated
alkylperoxides are remained largely unknown. We have
developed a more convenient and safe synthetic access to these
peroxides, which avoids the use of the highly reactive chlorine
trifluoride. Therefore we have revisited the reaction of known
perfluorinated hypofluorites[16] 2 in the presence of various metal
fluoride catalysts, see eq. 3.[17]
[
a]
M.Sc. J. H. Nissen, M.Sc. T. Stüker, T. Drews, Dr. S. Steinhauer, Dr.
habil. H. Beckers, Prof. Dr. S. Riedel
Fachbereich für Biologie, Chemie, Pharmazie,
Institut für Chemie und Biochemie – Anorganische Chemie,
Fabeckstraße 34/36, 14195 Berlin (Germany)
s.riedel@fu-berlin.de
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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COMMUNICATION
interactions (Figure S2.1). The shortest distances between the
fluorine atoms of two neighboring molecules of 297.8 pm is longer
than twice the van der Waals radius (F: 147 pm[22]). Molecular
structure parameters of 1a and 1b are summarized in Table S2.2
to S2.5. Some selected structure parameters of the fluorinated
2 3 2
peroxides (FO) , (F CO) , and 1a, 1b are compared in Table 1 to
those of their nonfluorinated counterparts. One important feature
of the molecular structures of 1a and 1b shown in Figure 1 is their
s-trans conformation of the COOC backbone with a dihedral angle
We finally found that perfluorinated alkylperoxides such as 1a and
the hitherto unknown bis(undecafluoro-tert-pentyl) peroxide

180°.
[
(C
up to 72 % by treatment of the hypofluorites (F
)(F C) COF (2b), respectively, with fluorinated silver wool at
50 °C (eq. 3, for experimental details see the Supporting
2
F
5
)(F
3
C)
2
CO]
2
(1b) can conveniently be obtained with yields
3
3
C) COF (2a) and
(
C
2
F
5
3
2
–
Information). At ambient temperatures these perfluorinated
peroxides are rather inert colorless liquids. Solid 1a melts at
1
9
8.4 °C and its boiling point is reached under decomposition at
9.0 °C, see SI.
We wanted to know if these perfluorinated peroxides can be
subject to an explosive decay and found that according to the U.N.
recommendations 1a is rather insensitive to both, impact (> 40 J)
and friction (> 360 N).[18]
Due to the low reactivity of these perfluorinated peroxides they
might be suitable as oxidation resistant reaction media e.g. in
halogenation reactions. We studied the reactivity of 1a towards
HF, HCl and HBr upon heating to 70 °C. Mixtures of 1a and
anhydrous HF show two liquid phases, but no reaction. While 1a
is stable towards HCl upon heating and irradiation in the gas
phase, the nonfluorinated counterpart, di-tert-butyl peroxide,
reacts with HCl vapour in a chain reaction involving free chlorine
atoms.[19] We also found no reaction of 1a at ambient
Figure 1. Single crystal molecular structures of the perfluorinated bisalkyl
peroxides 1a and 1b with thermal ellipsoids shown at the 50 % probability level
(top) and space-filling models (bottom).
Regarding the molecular structure of some simple peroxides
there is a long-standing contradiction between experimental and
computed gas-phase structures, which only very recently has
been partially solved.[6][23][24] This concerns primarily the dihedral
angle of these peroxides. Without interactions between the
substituents at the peroxo unit the COOC dihedral angle should
temperatures with elemental halogens such as F
after irradiation or heating to 50 °C 1a remained unchanged in the
presence of Cl and Br . The low reactivity of this perfluorinated
2 2 2
, Cl or Br . Even
2
2
peroxide agrees with its computed electrostatic potential map
shown in Fig. S3.1. While the electrostatic potential of
nonfluorinated di-tert-butyl peroxide suggests an easy attack of
the peroxy group by electrophiles, this group is well protected by
the bulky perfluorinated alkylgroups in 1a and 1b.
As expected, perfluorinated peroxides are oxidants. Accordingly,
DFT calculations at B3LYP/aug-cc-pVTZ level provide a rather
large adiabatic electron affinity of 1a of 373 kJ mol–1
be around 120°. A dihedral angle of about 120° was just
[6]
observed for the parent (HO)
stable perfluorinated peroxide (F CO) (GED:123(4))° ).
3 2
2
(MW:  = 119.8(10)° ) and the
[25]
The well-known peroxide skew structure was rationalized as a
compromise between several competing stereoelectronic effects
(
e. g. steric repulsion, electron pair repulsion and orbital inter-
[6]
,[6][26] (FO)
[24]
actions). Some simple peroxides such as (HO)
and (H
2 2
[23]
3
CO)
2
were shown to have non-rigid structures due to an
(
Table S3.2). Indeed, addition of ferrocene to liquid 1a yields
extremely flat potential energy minimum and/or large amplitude
torsion modes. Their experimental gas-phase structures obtained
quantitatively the ferrocenium nonafluoro-tert-butoxide (eq. 4).
The dark green solid product was well characterized by its
either by rotational spectroscopy (e.g. MW: r
electron diffraction (GED: structure) are derived from
vibrationally averaged parameters. For such non-rigid molecules
the experimental r /r structure may differ significantly from a
computed minimum structure, which in principle corresponds to
the equilibrium structure of a molecule (r structure). As shown for
a contradiction between an
0
structure) or
characteristic IR spectrum (Figure S1.1), which shows the known
r
a
III
]+ cation[20] and the alkoxide
vibrational modes for the [Fe Cp
2
3 3
anion [OC(CF )
][21].
0
a
e
[
6][26]
[24]
[23]
(
HO)
2
,
(FO)
2
,
3 2
and (H CO) ,
The first solid state structures of perfluorinated peroxides could
be obtained by in situ crystallization at the diffractometer, see
Figure 1. Compound 1a crystallizes at 283 K and 1b at 270 K.
Their structures were determined at 100 K where both
experimental and a computed structure were solved by computing
vibrational averaged structures. While the experimental gas-
[27]
phase structure of [(H
3
C)
3
CO]
2
suggest a non-planar COOC
structure
backbone, a recent study proved that the computed r
e
̅
compounds crystallize in the triclinic P1 group (Table S2.1) with
with a s-trans conformation of the COOC unit (  180°) is indeed
consistent with the previous experimental GED structure.
two molecules per unit cell for 1a. They form columns along the a
axis and layers along the c axis with no significant intermolecular
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COMMUNICATION
Table 1. Comparison of computed and experimentally obtained O–O bond
length (pm) and XOOX dihedral angles (°) for selected peroxides (RO) .
2
oxygen p-type lone pair with an anti-periplanar carbon centered
3
*(CX) orbital (X = F and CF , respectively).
Exp.
Calc.

The peroxide bond lengths (Table 1) correlates well with
dissociation energies for the homolytic O–O dissociation: the
longer the O–O bond lengths, the lower the bond dissociation
energy. Bond dissociation energies (BDE) computed at the
DLPNO-CCSD(T) level for selected peroxides are listed in
Table 2. These values are up to 5 % lower than those previously
ref.[a]
R
H
r(OO)

r(OO)
145.3
ref.
MW[6]
XRD/ND[
122.5
[6][26]
145.2(5)
46.1(3)
119.8(10)
90.2(4)
28]
1
GED[
29]
[24]
F
121.4(2)
21.7(5)
18.6(2)
88.1(4)
87.5(5)
88.3(1)
122.9
87.6
MW[
30]
[10]
1
1
derived at the CBS-QB3 from isodesmic and isogyric reactions,
however, they agree very well with the latest experimental values
XRD[
31]
CO) [
11]
CO]
[34]
(see Table 2). Earlier
135(5)[c]
GED[6]
180.0[c]
[23]
[b]
obtained for (F
experimental activation energies determined from rate constants
of the thermal decomposition obtained for [(H C) CO]
1632 kJ mol ) and 1a (1494 kJ mol1) were questioned
by more recent photoacoustic calorimetry study which
recommended
higher BDE of 179.64.5 kJ mol–1 for
.[34] The high-temperature activation energy for the
(H C) CO]
3
2
3
and [(H C)
3
2
H
3
C
145.7(12)
141.9(20)
148[d]
145.9
144.3
145.9
F
3
C
123.3(4)
GED[25]
124.3
150.1
3
3
2

1 [11]
[15]
(
tC
[27]
[b]
4
H
9
165.8(2.4)
164.0(4)
GED
XRD[
32]
a
1
47.8(3)
a
tC
F
F
147.9(2)
147.6(1)
180.0(5)
180.0(1)
XRD[b]
146.2
146.2
180.0
178.4
[b]
[b]
4
9
[
3
3
2
tC
XRD[b]
thermal decomposition of these non-rigid tert-butyl derivatives
might not be a good approximation for thermodynamic O–O bond
energies, also a redetermination of the rather low experimental
BDE for 1a needs to be considered (Table 2).
5
11
[
=
a] MW = microwave, XRD = X-ray diffraction, ND = neutron diffraction, GED
gas-phase electron diffraction.
[
[
[
b] This work (calc.: B3LYP-D3BJ/def2-TZVP).
c] For more details see text.
d] Fixed value.
Table 2. Comparison of O–O dissociation energies (in kJ mol–1) for the
reaction RO–OR
2 RO• of different peroxides.
R
Eel [a]
ΔG298 K [a]
BDE[b]
exp.
Molecular structures of the peroxides (F
3 2 3 3 2
CO) , [(H C) CO] and
F
3
C
212 (179)
186 (148)
179 (125)
158 (97)
142 (109)
114 (76)
101 (46)
78 (18)
199 (167)
170 (133)
164 (109)
143 (83)
1992[11]
179.64.5[34]
1494[15] [c]
-
1a have been calculated using different DFT and SCS-MP2
tC
H
9
methods together with an augmented triple zeta basis (def2-
TZVP; for Computational Details see the Supporting Information).
These methods provided consistent structural parameters (see
4
4
5
tC
F
9
Table S3.1) similar to those previously reported for (F
3
CO)
2
and
tC
F
11
11][33]
[
(H
3
C)
3
CO] [
2
. In Table 1, B3LYP-D3BJ/def2-TZVP results are
listed and compared to experimental values. While this method
provides reliable estimates for the dihedral angles of these
molecules, the O–O bond lengths, at least for the peroxides with
[a] Computed at the DLPNO-CCSD(T)/def2-QZVPP//B3LYP-D3BJ/def2-
TZVP level,[ in parentheses: B3LYP-D3/def2-TZVP level. [b] BDE(O–O) =
35]
2
H
298(RO•) − H298(RO–OR) at T = 298 K; H = U + k
B
T = Eel + EZPE + Evib +
E
rot + Etrans + k T. [c] For deviation between experimental and calculated
B
bulky tert-butyl groups [(H
3
C)
3
CO]
2
(147.8(3) pm) and 1a
values see text.
(
147.9(2) pm) are slightly underestimated.
The photolysis of both, (F
3
CO)
2
and 1a, was used in previous
CO
radicals, respectively. We have recorded
As mentioned above, one important feature of these peroxides is
an extremely flat computed torsional potential which exhibits
studies to produce the synthetically valuable fluorinated F
3
[
25][36]
[1][2]
3 3
and (F C) CO
either a very small trans barrier for [(H
3
C)
3
CO]
2
(see Figure S3.2)
gas-phase UV/Vis spectra of these perfluorinated alkylperoxides
or a marginal trans minimum for 1a (Figure S3.3). This general
in the wavelength range 200 – 800 nm. In Figure 2 only the region
feature is due to competing and mutually balancing stereo-
3 2
up to 400 nm is shown. The lowest energy transition of (F CO) is
electronic effects.[6] The short O–O bond lengths in (FO)
is
below 200 nm while 1a and 1b show weaker red-shifted UV
transitions at 253 and 250 nm, respectively. According to
preliminary TD-DFT calculations (Table S3.2) these lowest
energy transitions almost exclusively correspond to HOMO-
LUMO (n*) excitations. In agreement with previous studies[
the photodecomposition of 1a using a 1000 W Xenon high
2
commonly explained by a stabilizing orbital interaction of the
oxygen p-type lone pair with an anti-periplanar antibonding
*(OF) orbital. Such an anomeric orbital interaction is favored in
34]
the planar s-trans conformation of 1a, however, its rather long O–
O bond length indicates considerable steric repulsion of the bulky
perfluoro tert-butyl substituents, well recognizable by the
spherical model of 1a shown in Figure 1 (bottom). On the other
side, the computed C–O bond lengths (see Table S3.1) of the
pressure lamp in a quartz vessel yields quantitatively (F
3 2
C) CO
and C
2 6
F .
3 2
perfluorinated peroxides (F CO) (139.9 pm) and 1a (140.7 pm)
are significantly shorter than those of the non-fluorinated
3 2 3 3 2
analogues (H CO) C) CO] (146.0 pm),
(142.0 pm)[ and [(H
23]
which is consistent with a preferred anomeric interaction of the
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Angewandte Chemie International Edition
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COMMUNICATION
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0
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Figure 2. Gas-phase UV/Vis spectra (10 cm cell) of the perfluorinated bisalkyl
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[
(
F
3
C)
3
COF (2a) and (C
2
F
5
)(F
3
C)
2
COF (2b). Their solid state
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4
structures feature rather long peroxide bonds and an unusual
s-trans conformation along the COOC backbone with a dihedral
angle  180°. The molecular structures and O–O bond energies
are compared to those of the nonfluorinated analogous. Their
resistance against oxidizing and halogenating reagents as well as
their insensitivity to impact and friction make these liquid
perfluorinated peroxides interesting solvents for halogenation
reactions.
[
[
9
[
[
[
17] R. C. Kennedy, G. H. Cady, J. Flourine Chem. 1973, 3, 41–54.
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[
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The authors gratefully acknowledge support of this research by
the Deutsche Forschungsgemeinschaft (DFG) under the projects
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also gratefully acknowledge support of the Soroban high-
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4
Keywords: Peroxides • Fluorine Chemistry • Hypofluorites •
Molecular Structure • Quantum-Chemical Calculations
1
[
37] Recommendations on the transport of dangerous goods.
Model regulations, UNITED NATIONS, New York, 2007.
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