Hydrogen/Deuterium-Exchange Reactions of Methane with Aromatics and Cyclohexane Catalyzed by a Nanoscopic Aluminum Chlorofluoride

Article abstract of DOI:10.1002/cctc.201701327

H/D-exchange reactions between methane and deuterated solvents such as [D₆]benzene and [D₁₂]cyclohexane were heterogeneously catalyzed by nanoscopic aluminum chlorofluoride (ACF=AlCl_xF_3?x, x≈0.05–0.3) under very mild conditions. ¹³C NMR spectroscopy experiments at labeled methane revealed the formation of all isotopologues. AlCl₃, AlBr₃, HS-AlF₃, γ-Al₂O₃, and γ-Al₂O₃ preheated at 700 °C did not show any H/D-exchange reaction of methane or [D₆]benzene. Mechanistically, electrophilic activation of methane was suggested at the ACF surface.

Full text of DOI:10.1002/cctc.201701327

Accepted Article
Title: H/D Exchange Reactions of Methane with Aromatics
and Cyclohexane Catalyzed by a Nanoscopic Aluminum
Chlorofluoride
Authors: Thomas Braun, Beatriz Calvo, and Erhard Kemnitz
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To be cited as: ChemCatChem 10.1002/cctc.201701327
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10.1002/cctc.201701327
ChemCatChem
COMMUNICATION
H/D Exchange Reactions of Methane with Aromatics and
Cyclohexane
Catalyzed
by
a
Nanoscopic
Aluminum
Chlorofluoride
Beatriz Calvo,[a] Thomas Braun,*[a] and Erhard Kemnitz*[a]
Dedication ((optional))
Abstract: H/D exchange reactions between methane and
alkanes[9] or aromatics[10] and although these results are
promising, methane activation either in the homogeneous[11] or
heterogeneous phase needs further developments of catalytic
systems as a well as a deeper understanding of reaction
mechanisms.[12]
deuterated solvents such as bezene-d6 and cyclohexane-d12 are
heterogeneously
catalysed
by
a
nanoscopic
aluminium
chlorofluoride (ACF
=
AlClxF3-x x ≈ 0.05-0.3) under very mild
conditions. 13C NMR experiments at labeled methanes reveal the
formation of all isotopologues. AlCl3, AlBr3, HS-AlF3, γ-Al2O3 and γ-
Al2O3 preheated at 700 °C did not show any H/D exchange reaction
of methane and benzene-d6. Mechanistically, an electrophilic
activation of methane is suggested at ACF.
ACF (AlClxF3- x ≈ 0.05-0.3) is an amorphous, microporous
x
Lewis-acidic material with a highly distorted structure and a large
surface area (> 100 m2/g), which is capable of catalyzing unique
reactions.[13]
hydrodefluorination,
The
conversions
hydrodechlorination,
involve
hydroarylation,
dismutation,
dehydrofluorination and C-H activation reactions of alkanes.[13]
For the latter H/D exchange of cyclic alkanes with deuterated
benzene has been achieved.[14] This paper reports H/D
exchange catalyzed by ACF under very mild conditions between
the aromatics toluene-d8 or benzene-d6 and methane, as well as
between the two alkanes cyclohexane-d12 and methane.
Methane is a small and often rather inert molecule that is the
major component of natural gas. The abundant reserves of this
light hydrocarbon together with the rapid depletion of petroleum
reserves have led to an increasing interest in the utilization of
methane as energy carrier and feedstock for the production of
high value chemicals by the development of new reaction routes
in C1 chemistry.[1] The petrochemical industry converts methane
on using high energy consuming processes such as steam
reforming which leads to an oxidation of the C-H bonds to give
mixtures of CO and H2 from which higher hydrocarbons and their
derivatives can be produced.[2] This is a well know industrial
technology, but concerning sustainability the stream reforming is
an old non-efficient process. Thus, the utilization of methane to
its full potential remains a significant challenge for academia and
industry.[3]
Some catalytic processes in which methane is oxidized
selectively to methanol are based on Shilov-type chemistry.[4]
The reactions take place in homogeneous phase and they
involve the electrophilic activation of CH4 at PtII centers to
produce a PtII-CH3 species.[5] It is possible to oxidize methane to
methyl bisulfate in sulfuric acid with high turnover frequencies
(>25,000 h-1), on using K2PtCl4 as catalytic precursor. The
difficult separation of the product and the recycling of sulfur
dioxide preclude the industrial implementation of this important
catalytic process.[6]
The reaction of benzene-d6 with 13CH4 at 70 °C in screw-capped
NMR tubes in the presence of catalytic amounts of ACF gave
mono- to fully deuterated methanes as H/D exchange products,
as well as tetra- and penta-deuterated benzene (Scheme 1).
Likewise, the successful deuteration of methane was
accomplished by using toluene-d8 and reactivity was observed at
aromatic C-D bonds and at the CD3 group. Note that with
deuterated benzene the exchange reaction also takes place at
room temperature reaching a conversion of 39 % (Table 1). It is
remarkable that under the same mild conditions, H/D exchange
to methane was also obtained on using cyclohexane-d12 as
deuterium source. Note further that for the H/D exchange with
deuterated cyclohexane, partially deuterated cyclohexane as
well as methylcyclohexane were generated; the isomerization of
cyclohexane at ACF was described previously.[14]
At a heterogeneous phase, catalytic oxidation of methane has
been accomplished by various metal modified zeolites as well as
metal oxides.[7] Copéret et al. used pre-heated γ-Al2O3 at 700°C
as one of the most active oxides capable of catalyzing
processes to study H/D exchange reactions of CH4/CD4 mixtures
or D2/CH4.[8] There are also reports on oxidative coupling of
methane at metal oxides, including its efficient conversion to
Scheme 1. H/D exchange between methane and deuterated solvents
catalyzed by ACF.
The H/D exchange reactions were monitored by 1H and 13C
NMR spectroscopy, and the results of the catalytic conversions
and TOFs are listed in Table 1. In the 13C{1H} NMR (inverse-
gated decoupled) spectra the signals for the deuterated
methane species 13CDxH4-x (x = 1, 2, 3, 4) were integrated to
determine their ratios. The spectrum for the exchange reaction
with C6D6 was compared with a simulated 13C NMR spectrum,
which confirms the ratios of the deuterated species (Table 1 and
Table S3 (SI)).
[a]
Dr. B. Calvo, Prof. Dr. Braun, Prof. Dr. E. Kemnitz
Humboldt-Universität zu Berlin
Book-Taylor-Straße2
12489 Berlin (Germany)
E-mail: thomas.braun@cms.hu-berlin.de;
erhard.kemnitz@chemie.hu-berlin.de
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701327
ChemCatChem
COMMUNICATION
To study the scope of the H/D exchange reaction further, ethane
and propane were tested in the presence of C6D6. In these
reactions, the alkane was bubbled through benzene-d6 in the
presence of catalytic amounts of solid ACF, which was
suspended in the NMR tube. Table 2 shows the reaction times
and conversions. Ethane and propane underwent H/D exchange
giving mixtures that contained a range of deuterated products to
yield mono- to fully- deuterated alkanes (SI). No exchange
reaction between H2 and benzene-d6 was observed.
Table 2. Deuteration of ethane and propane catalyzed by ACF, using
benzene-d6 as deuterium source.
entry
substrate
ethane
time (days)
conv/%[a]
1
2
4
4
80
50
propane
Figure 1. 13C{1H} ig NMR spectrum of H/D exchange between methane and
benzene-d6 catalyzed by ACF.
[a] alkanes were bubbled into the reaction solution for 5 min which contained
ACF (25 mg, 25 μmol) in 0.5 ml benzene-d6. The NMR tube was afterwards
sealed. The conversions were determined by 1H NMR spectroscopy using
CD2Cl2 as external standard in a capillary.
The data in Table 1 also show that the conversions for the
deuteration of methane were comparable on using either
benzene-d6 or cyclohexane-d12 as deuterium sources, although
the reaction times were longer in the case of the cyclic alkane.
The activities for the H/D exchange reactions at benzene-d6,
toluene-d8 and cyclohexane-d12 are similar, affording
comparable amounts of mono-, di-, tri- and tetra-deuterated
methanes for benzene-d6. Cyclohexane-d12 afforded CH3D and
CH2D2 as the major species; whereas the use of toluene-d8 as
source of deuterium resulted in CH3D being the major
deuterated methane.
In order to compare the activity of ACF in the H/D exchange
reaction of methane with benzene-d6, we tested other
conceivable catalysts such as AlCl3, AlBr3, HS-AlF3 (high-surface
AlF3) and γ-Al2O3 as well as the pre-heated γ-Al2O3 at 700 °C.
None of these materials were capable of catalyzing the H/D
exchange reaction between benzene-d6 and methane under the
same conditions as used for the catalytic reactions at ACF.
In order to determine potential interactions between ACF and
the reactants, CH4, C6H6 and C6H12, Pulse Thermogravimetric
Analyses (PulseTA® P-TGA) were performed (SI). Figure 2
illustrates the experiment in which methane and benzene were
alternately exposed to ACF (or an analogous experiment with
cyclohexane see SI, Figure S7). The data show that consecutive
injections of methane gas do not lead to mass or temperature
changes (pulses 1-3 in Figure 2). The subsequent addition of
benzene (pulse 4-6) results in mass increase and exothermic
responses, demonstrating that the arene undergoes adsorption
at the ACF surface. This benzene-modified ACF material does
not respond to further injections of methane (pulses 7-9). The
PulseTA® experiments support that benzene and cyclohexane
(SI, Figure S7) interact strongly with the nanoscopic amorphous
ACF matrix,[13a)] whereas methane is not adsorbed. Similar
results were obtained for preheated γ-Al2O3 (SI, Figure S8).
Interestingly, ACF pre-treated with deuterated or non-deuterated
benzene, and which was subjected to vacuum for 48h, did not
catalyze the H/D exchange reaction when methane or
deuterated methane was exposed to the solids in benzene-d6 or
C6F6. Apparently, pre-treating ACF with benzene results in an
irreversible blockage of catalytic sited.
Table 1. Deuteration of methane catalyzed by ACF.
entry
solv.
T
/ºC
conv
/%[a]
TOF
(h-1)
Products, ratios
CH3D
CH2D2
CHD3
CD4
1
2
3
4
5
C6D6
C6D6
C6D6
Tol-d8
C6D12
25
110
70
39
57
77
82
78
57
83
-
-
-
-
-
-
-
-
112
119
113
1
1
1
0.8
0.5
0.8
0.8
0.4
0.4
1.1
0.2
0.1
70
70
[a] 10 psi of 13CH4 (0.014 g, 0.87 mmol), ACF (25 mg, 25 μmol) and 0.5 ml
of deuterated solvent at 70 ºC. The conversions and TOFs were
determined by 1H NMR spectroscopy using CD2Cl2 as external standard
and the ratio of deuterated species in the 13C{1H} inverse-gated spectrum
after 24 hours. The ratios of deuterated products were calculated by
integration of individual product signals.
Figure 2. PulseTA® curves of alternating injections of CH4 (pulses 1-3), liquid
benzene (pulses 4-6), and again CH4 (pulses 7-9) onto 29.3 mg of ACF in Ar.
The black and blue ion current curves correspond to the m/z mass numbers of
16 (CH4+ for methane) and 78 (C6H6+ for benzene).
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10.1002/cctc.201701327
ChemCatChem
COMMUNICATION
Mechanistically, we suggest an electrophilic activation of
methane at Lewis-acidic aluminum centers at ACF, although the
PTA experiments do not indicate any interaction of methane with
ACF. However, in solution rapid equilibria involving an
adsorption of methane molecules is conceivable. Such an
interaction would allow an electrophilic activation of methane
and a reversible cleavage of the C–H bond via protonation and
benzene-d6, toluene-d8 or cyclohexane-d12 (Scheme 2).[8b,15] The
latter steps are reminiscent of benzonium formation in super
acids where C6H6 behaves as base to form C6H7+ as reported by
Olah et al. [16] Furthermore, the basic fluorine atoms bound at the
ACF surface could support an electrophilic C-H activation of
methane and shuttle protons to the solvent molecule.[17]
Comparable reaction pathways have been suggested for
methane activation reactions at zeolites.[18] The C–H activation of
methane at preheated Al2O3 is enabled by surface Lewis acid-
base pairs. [8c]
The generation of species with methenium-like character at the
ACF surface is less likely, because for H/D exchange at
benzene or toluene the formation of the Friedel-Crafts products
was not observed. Note that ACF can catalyze Friedel-Crafts-
type reactions.[13] It should also be noted that ACF always
contains some Brønsted acidic centers, because the surface
immediately interacts with adventitious water. It therefore can’t
be entirely excluded that any surface protons may be involved in
any H/D exchange reaction by protonation of anionic like methyl
groups. The protonation of methane to yield methonium-like
species would presumably produce H2, which was not observed.
However, when wet benzene-d6 was used as solvent in a
catalytic set-up with CD4 incorporation of hydrogen atoms of the
water into the methane was observed, but not into benzene.
This demonstrates that the ACF surface can induce an H/D
exchange between very small amounts of water and methane.
The conversions resemble electrophilic methane activation and
H/D exchange reactions between methane and Brønsted
centres at some zeolites.[19] However, importantly, a catalytic
H/D exchange between CH4 and C6D6 in wet C6D6 was also
oberved. Note, that with larger amounts of water ACF becomes
irreversibly destroyed.[20]
capability for the activation of C–H bonds in methane resulting in
H/D exchance reactions between deuterated aromatics or
cyclohexane-d12. AlCl3, AlBr3, HS-AlF3, γ-Al2O3 and preheated γ-
Al2O3 do not show such a reactivity under the same conditions.
Mechanistically an electrophilic activation of methane is
presumed at the Lewis-acidic surface sites, although the binding
properties of benzene are better than those of methane.
Acknowledgements
Support from the research training group “Fluorine as a Key
Element” as well as the cluster of excellence “Unifying Concepts
in
Catalysis”
both
funded
by
the
Deutsche
Forschungsgemeinschaft is gratefully acknowledged. We thank
Dr. Feist for the Pulse Thermogravimetric Analysis (PTA) and L.
Ahrem, C. Marshall and V. Scalise for the synthesis and
preparation of some of the catalysts used in this work.
Keywords: aluminum • fluoride • methane • heterogeneous
catalysis • H/D exchange reactions
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10.1002/cctc.201701327
ChemCatChem
COMMUNICATION
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COMMUNICATION
Beatriz Calvo, Thomas
Braun,* and Erhard
Kemnitz*
Nanoscopic aluminium chlorofluoride (ACF) exhibits an excellent catalytic activity in the H/D
exchange reaction of CH4 and deuterated arenes or cyclohexane that results from the interaction
of strong Al Lewis acid centers and the reactants at the ACF surface.
Page No. – Page No.
H/D
Exchange
Reactions of Methane
with Aromatics and
Cyclohexane
Catalyzed
by
a
Nanoscopic Aluminum
Chlorofluoride
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