Dynamic Covalent Chemistry under High-Pressure:A New Route to Disulfide Metathesis

Article abstract of DOI:10.1002/chem.201801740

This work describes, for the first time, the application of combined pressure and temperature stimuli in disulfide metathesis reactions. In the system studied, above a pressure of 0.2 GPa, equimolar amounts of symmetric disulfides bis 4-chlorophenyl disulfide [(4-ClPhS)₂] and bis 2-nitrophenyl disulfide [(2-NO₂PhS)₂] react to give the heterodimeric product 4-Cl-PhSSPh-2-NO₂. In contrast to experiments conducted in solution at atmospheric pressure or in mechanochemical experiments under ball-mill grinding conditions, there is no necessity to use a base or thiolate anion as a catalyst for the exchange reaction under investigated conditions. Single-crystal and powder X-ray diffraction revealed also that, despite the high-pressure conditions of this reaction, the heterodimeric-disulfide product unexpectedly crystallizes into the low-density polymorph A. This counterintuitive result contrasts with the high-pressure stability of the higher-density polymorph B, confirmed by its compression up to 2.8 GPa with no signs of a phase transition.

Full text of DOI:10.1002/chem.201801740

A Journal of
Accepted Article
Title: Dynamic Covalent Chemistry under High-pressure: a New Route
to Disulfide Metathesis
Authors: Szymon Sobczak, Wojciech Drożdż, Giulio Lampronti,
Anna Belenguer, Andrzej Katrusiak, and Artur Ryszard
Stefankiewicz
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
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To be cited as: Chem. Eur. J. 10.1002/chem.201801740
Link to VoR: http://dx.doi.org/10.1002/chem.201801740
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COMMUNICATION
Dynamic Covalent Chemistry under High-pressure: a New Route
to Disulfide Metathesis
Szymon Sobczak , Wojciech Drożdż [a,b], Giulio I. Lampronti [c,d], Ana M. Belenguer , Andrzej
[
a]
[d]
Katrusiak *[a], Artur R. Stefankiewicz *[a,b]
Abstract: We describe here for the first time the application of
combined pressure and temperature stimuli in disulfide metathesis
reactions. In the system studied, above a pressure of 0.2 GPa
equimolar amounts of symmetric disulfides bis 4-chlorophenyl
disulfide [(4-ClPhS)
2
] and bis 2-nitrophenyl disulfide [(2-NO
2 2
PhS) ]
react to give the heterodimeric product 4-ClPhSSPh2-NO
2
. In contrast
to experiments conducted in solution at atmospheric pressure or in
mechanochemical experiments under ball-mill grinding conditions,
there is no necessity to use a base or thiolate anion as a catalyst for
the exchange reaction under investigated conditions. Single-crystal
and powder X-ray diffraction revealed also that despite the high-
pressure conditions of this reaction the heterodimeric-disulfide
product unexpectedly crystallises into the low-density polymorph A.
This counterintuitive result contrasts with the high-pressure stability of
the higher-density polymorph B, confirmed by its compression up to
2.8 GPa with no signs of a phase transition.
Figure 1. Generation of disulfide structures via four different synthetic
methodologies: a) in solution; b) under liquid assisted grinding (LAG) conditions;
c) under neat grinding (NG) conditions; d) under high-pressure conditions.
There is ongoing demand for the development of stimuli-
responsive materials, and a great deal of work has been
dedicated to the generation of molecular and supramolecular
systems that can be crafted into functional smart materials.[1]
Investigation of stimuli-responsive molecular behavior can
facilitate better understanding of biological systems but also
accelerate the development of artificial "intelligent" materials
capable of reversible structural, electronic and chemical
modification in response to an external stimulus, such as
temperature, pH or light.[2] In this context, the emergence of
Dynamic Covalent Chemistry (DCC) has substantially influenced
chemical synthesis, with the concept relying on the
formation/breakage of reversible covalent bonds in response to
the external environment.[3] Among various dynamic covalent
bonds, those of disulfides are important due to their pivotal roles
in biology, for example in stabilization of the secondary structures
of proteins.[4] Although disulfides are relatively stable, the kinetics
of their production, reduction, isomerisation and interconversion
reactions are highly pH-sensitive, commonly
attaining maximum rates in the pH range 7-9. In biological
systems, many disulfide exchange processes are controlled and
catalyzed by delicate enzyme machineries, providing elegant
examples of one form of DCC. In the usual solution state,
thiol/disulfide exchange involves nucleophilic displacement (S 2)
N
of the thiolate anion from the disulfide (cleavage of the original S–
S bond), through attack by another thiolate anion and finally
protonation of the liberated thiolate moiety.[5] Another exchange
mechanism involving homolytic cleavage to give radicals followed
[6]
by the recombination of disulfide bond is also possible.
The reversibility of disulfide bonds has been exploited in the
construction of many complex functional architectures e.g.
macrocycles, catenanes, knots, cages and self-replicating
systems.[
4,
7]
The synthesis of functional disulfide molecular
systems displays great sensitivity to external stimuli (physical or
chemical), which can significantly alter the position of the reaction
equilibrium.[8] The most widely used chemical stimuli involve the
use of template molecules or pH.[9] The Ramström group showed
that disulfide exchange is possible by application of phosphine[10],
while the group of Pittelkow discovered exchange between
diselenides and disulfides at neutral pH[11]. On the other hand,
Alfonso et al. showed the effect of DMSO on the thiol-disulfide
exchange.[12] Physical stimuli include, light, temperature,
ultrasound or pressure and while the first three have been
previously employed,[13] to the best of our knowledge, no
investigation into exchange of disulfides under high-pressure
conditions has been published.
The application of pressure as a variable in chemical
studies can lead to the discovery of new materials with unique
properties and can provide an efficient means of modifying the
structure of crystals.[14] Within a relatively low pressure range of
a few GPa the volume of molecular crystals can be compressed
[
a]
S. Sobczak, W. Drożdż, Prof A. Katrusiak, Dr A. R. Stefankiewicz
Faculty of Chemistry, Adam Mickiewicz University,
Umultowska 89b, 61-614 Poznań, Poland
Email: katran@amu.edu.pl, ars@amu.edu.pl
W. Drożdż, Dr A. R. Stefankiewicz
Centre for Advanced Technologies, Adam Mickiewicz University,
Umultowska 89c, 61-614 Poznań, Poland
G. I. Lampronti
Department of Earth Sciences, University of Cambridge, Downing
St, Cambridge, CB2 3EQ (UK)
A. M. Belenguer, G. I. Lampronti
Department of Chemistry, University of Cambridge,
Lensfield Road, Cambridge, CB2 1EW (UK)
[b]
[c]
[d]
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.

Chemistry - A European Journal
10.1002/chem.201801740
COMMUNICATION
by as much as 80% and molecular conformations and
intermolecular interactions can be markedly changed.
Consequently, pressure has been used for generating new
polymorphs,[15] new solvates[16] and new reaction pathways when
activation volumes differ.[17] In particular, diamond-anvil cell high-
pressure experiments have been employed in the transformations
of intramolecular contacts,[18] formation of new coordinate
reaction of two homodimers under LAG and NG conditions which
resulted in the generation of two different polymorphs of the
heterodimeric product 4-ClPhSSPh2-NO
polymorph A (CSD refcode FUQLIM01, space group P2
2
, namely: low density
/n) and
1
high density polymorph B (CSD refcode FUQLIM, space group P-
1). The former was generated under ball mill NG conditions while
polymorph B was formed under ball mill LAG conditions where a
bonds,[19] or conformational conversions
in disulfide
few drops of MeCN (>23L per 200mg) were added to the
compounds.[ This indicates that exchange reactions of weakly
bound species could be triggered by the application of pressure
only, leading to a new, unexplored, catalyst-free, high-pressure
DCC field.
20]
powder.
[21, 25]
The reaction yield is 50% in solution, while it is over
97% under mechanochemical conditions. These studies have
also demonstrated a thermodynamic control of the product
Here we report a new approach to the disulfide-exchange
reaction, in which high pressure was used as a physical stimulus
in the reconfiguration process within DCC. We have shown that
above the pressure of 0.2 GPa equimolar amounts of symmetric
disulfide homodimers: [(4-ClPhS)
absence of base catalyst to give the heterodimeric product 4-
ClPhSSPh2-NO . To the best of our knowledge this is the first
2 2 2
] and [(2-NO PhS) ] react in the
2
Figure 2. High-pressure DAC chamber disulfide exchange experiment; (a)
example where high pressure imposed at a mildly elevated
temperature has been used to promote a disulfide exchange
reaction under non-basic and non-reducing conditions. The use
of the diamond-anvil cell (DAC) chamber in the conducted
experiments made it possible not only to work under high
pressure conditions but also to control the temperature of the
reaction, which proved to be necessary to dissolve the reaction
substrates.
2 2 2
mixture of crystals of both homodimers ([(4-ClPhS) ] and [(2-NO PhS) ],
encircled in green and blue, respectively) and a ruby chip for pressure
calibration (encircled red) in IPA at 0.2 GPa/ 296 K; (b) reaction mixture at 330
K
showing completely dissolved [(4-ClPhS)
heterodimer 4-ClPhSSPh2-NO (encircled yellow) at 0.1 MPa/ 296 K (an air
bubble testifies to the released pressure); photos from taken in experiment No.
(ESI Section 4.2.3)
2
]; (c) crystals of generated
2
3
distribution: the relative stabilities of the two polymorphs have
been shown to be affected by crystal surface solvation coupled
with the nanosize nature of the milled powder. These
thermodynamic concepts are general and apply to all systems.[
For the purpose of investigating the disulfide exchange
reaction under high pressure conditions several solvents were
tested, of which 2-propanol (IPA) proved to give the best results
both in terms of single crystal quality of the product and reaction
yield quantification, as explained below (Fig. 2 and ESI 4.2).
Because of the small quantities of substrates contained in the
DAC chamber, we used the methods of powder and single-crystal
diffraction for identifying the products recovered after the
reactions. In a typical experiment, an equimolar mixture of
2
The formation of heterodimeric product 4-ClPhSSPh2-NO was
investigated via four distinct synthetic methodologies (Fig.1). In
general, the metathesis of aromatic disulfides is not spontaneous
and requires a base catalyst (DBU, 1,8-diazabicycloundec-7-ene
was used in the present studies). In solution state, the reaction
25b]
between equimolar amounts of two homodimers [(4-ClPhS)
(2-NO PhS) ], in the presence of base (DBU) led to a mixture of
the initial substrates and the heterodimeric product 4-
2
] and
[
2
2
[
21]
ClPhSSPh2-NO
same reaction was further explored under liquid assisted grinding
LAG) and neat grinding (NG) conditions (Fig.1b and 1c). It has
been shown that in the solid suspension in slurry at
.1 MPa/300 K and in the solid state under milling conditions, the
thermodynamic equilibrium DCC:
4-ClPhS) + (2-NO PhS) = 2(4-ClPhSSPh2-NO
2
in the statistical 1 : 1 : 2 ratio (Fig. 1a). The
(
0
2 2 2
homodimers [(4-ClPhS) ] and [(2-NO PhS) ] was added at room
temperature to an appropriate solvent and loaded into a DAC
chamber at appropriate concentrations, where disulfide exchange
under high-pressure conditions was investigated (Fig. 2a, for
detailed experimental procedures see chapter 4 in the ESI). The
lowest pressure at which reaction between two homodimers
occurred was 0.2 GPa. The solubility of both homodimers, ([(2-
(
2
2
2
2
)
lies very much to the right, with often mole fraction exceeding 95%
of heterodimer in the reported experiments.[21,25] The results that
we here present suggest that this holds also at high pressure. Due
to experimental constraints, we were not able to determine for
certain whether this reaction achieved thermodynamic equilibrium
DCC composition in the solid precipitate in any of the experiments
presented. However, the fact that the homodimers react to give
the heterodimer shows that under high pressure conditions such
thermodynamic equilibrium DCC composition can in principle be
achieved even in the absence of a catalyst.
NO
2
PhS)
2
] being generally significantly less soluble than [(4-
ClPhS)
2
]), under these conditions was found to be several times
lower than that under ambient conditions. Initially, the reaction
mixture was heated to 330 K causing dissolution of homodimer
[
2 2 2
(4-ClPhS) ] (Fig. 2b) while the second component [(2-NO PhS) ]
was dissolved at 349 K. The reaction mixture thus prepared was
heated at 323 K for 5 h after which it was gradually cooled to room
temperature and the pressure was released to 0.1 MPa. This led
to precipitation of a crystalline material (Fig. 2c), which was
recovered from the DAC and characterized by single-crystal X-ray
diffraction measurements. The unit-cell dimensions and space-
group symmetry unequivocally showed the exclusive formation of
Mechanochemistry using manual or ball mill grinding equipment
is emerging as an attractive and sustainable synthetic tool.[22]
LAG, a technique which consists of grinding solid materials in the
presence of a few drops of solvent, has dramatically broadened
the applications of mechanochemistry;[23] LAG often accelerates
reaction kinetics and indeed sometimes yields different outcomes
[
21, 24]
to NG techniques.
We extensively investigated the exchange
2
the heterodimeric disulfide product 4-ClPhSSPh2-NO .
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Furthermore, the product was obtained solely in the form of low
density polymorph A. In order to eliminate the possibility of the
presence of any ingredients acting as the catalyst promoting the
heterodimer, all high-pressure reactions were repeated on super-
clean substrates and the consistent results have been obtained.
The high-pressure synthesis experiments were performed at
various pressures (from 0.18 to 0.85 GPa), temperatures (from
To further characterise the nature of the reactions, we
investigated the possibility of phase transition between
low-density polymorph A and high-density polymorph B of
heterodimer 4-ClPhSSPh2-NO
For the high-pressure in-situ experiments, crystals of heterodimer
4-ClPhSSPh2-NO in the polymorph B form were used. We
2
under high pressure conditions.
2
employed a Merrill-Bassett DAC, modified by mounting the
diamond anvil directly on steel supports with conical windows.[
The gaskets were made of steel foil, 0.3 mm thick, with spark-
eroded 0.4 mm holes. Pressure was calibrated by the R1 ruby-
line shift, measured by a Photon Control Spectrometer affording
0.02 GPa accuracy.[27] The structure of polymorph B was refined
starting from its ambient-pressure structure[28] by full-matrix least
squares fitting with SHELXL;[29] the Olex2 interface was used.[30]
The unit-cell parameters of polymorph B decreased monotonically
up to 2.8 GPa (Fig. 4, see ESI for details) and no phase transitions
were observed.
26]
296 to 495 K, increased till almost all of the substrates were
dissolved) and in three different solvents: 2-propanol (IPA),
methanol and acetonitrile. Experiments carried out under various
reaction conditions were aimed at investigating their effect on the
form of the product obtained as well as generation of possibly best
quality material for X-ray analysis. We established that the solvent
used for the high-pressure reactions significantly affects the final
form of the product. When IPA was employed the product
precipitated in the form of single crystals of heterodimer 4-
ClPhSSPh2-NO
other hand, the reaction in acetonitrile yielded only very small
crystals of 4-ClPhSSPh2-NO , however in this case, a mixture of
both polymorphs A and B were identified in a series of single-
crystal diffraction measurements. Unfortunately, despite
2
solely as polymorph A (see ESI 4.2). On the
Heterodimeric polymorphs A and B display a significant
density difference of 1.554 and 1.61925 gcm at 0.1 MPa
respectively, suggesting that polymorph B should be more stable
at high pressure than polymorph A.[31] In terms of the average
compression of molecular crystals, this difference of 0.020 g cm-3
is usually generated by about 0.15 GPa. Nonetheless, despite the
high-pressure conditions, we obtained the heterodimer in the form
of low-density polymorph A. As well, our experimental data show
that polymorph B does not convert into polymorph A at high
pressure. Therefore, it is plausible that the reaction product
nucleated in the form of low-density polymorph A, in accordance
with Ostwald's rule of stages, despite the is simply metastable
state under the high-pressure conditions.
-3
2
a
number of attempts (various reaction conditions were tested,
namely distinct concentrations, pressures, temperatures and
incubation times) to grow single crystals from the material
generated in the reaction in methanol, only fine powders were
obtained (see ESI 4.3).
2
Figure 3. X-ray diffraction patterns of heterodimer 4-ClPhSSPh2-NO a) in the
form of polymorph B (marked as red); b) in the form of polymorph A (marked as
blue) superimposed with the data obtained from the material collected from the
experiment at high pressure (marked as orange).
Figure 4. Heterodimer in polymorph B with indicated changes of torsion angles
between 0.1 MPa and 2.8 GPa.
To confirm the results obtained by means of single-crystal
X-ray crystallography, an additional experiment was performed in
which we collected the polycrystalline material obtained in the
DAC chamber with IPA as a solvent and gathered it with
immersion oil on a nylon loop. A 1-D powder pattern (see Fig.
S22a in the ESI) was obtained by integrating the frames collected
over 2θ. A Rietveld refinement performed on this pattern after a
background subtraction (see Fig. S22b in the ESI) showed that
the polycrystalline material was predominantly polymorph A. The
so obtained PXRD pattern is also here compared to those of
polymorph A (blue) and B (red) (Fig. 3). It is clear that polymorph
B does not match the experimental pattern.
At the present stage of the study, two explanations of these
results are possible. In the first scenario, at 150 MPa and above
400 K polymorph A becomes more stable than polymorph B.
Under these conditions the heterodimer product precipitates in
the form of the more stable polymorph A. When the temperature
is lowered at isochoric conditions polymorph B becomes more
stable, but the heterodimer crystals continue to grow in the form
of nucleated form A, in the absence of any seeds of polymorph B.
Consequently, despite the high-pressure preference of polymorph
B at 20ºC, polymorph A is obtained instead.
Alternatively, polymorph B is more stable than polymorph A
throughout the high-pressure high-temperature range. Then the
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Chemistry - A European Journal
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COMMUNICATION
nucleation of the low-density polymorph A occurs according to
Ostwald’s rule of stages.[32] Polymorph A has been proved to be
more stable than polymorph B when the crystal size is in the range
of tens of nm at ambient pressure. [22b] When the DAC is cooled,
the crystals grow in this nucleated form in isochoric conditions
down to room temperature and the heterodimer product is
recovered in the form of the metastable polymorph A.
We have successfully applied a new approach to disulfide
exchange reactions by using the effect of pressure instead of
catalytic/reducing agents. Particular conditions of pressure and
temperature allow an equimolar mixture of the symmetrical
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exclusively the heterodimer 4-ClPhSSPh2-NO
2
]
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2
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in the absence of
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2
any base catalyst in a range of solvents. The purchased
homodimers were purified by recrystallisation (see ESI 1.1) for the
experiments here discussed. Therefore, we exclude that the
phenomena observed could possibly be explained by some
contaminant acting as a catalyst at high temperature and/or
pressure. The absence of a catalyst is remarkable, as it proves
that the reaction proceeds under the influence of physical stimuli
only. Therefore, the experimental results here presented show
that supercritical or close to supercritical conditions are
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pressure and high temperature routes for DCC processes
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20] S. Sobczak, A. Katrusiak, J. Phys. Chem. C 2017, 121, 2539-2545.
21] A. M. Belenguer, T. Friscic, G. M. Day, J. K. M. Sanders, Chem. Sci.
We thank National Centre for Research and Development (grant
LIDER/024/391/L-5/13/NCBR/2014) for financial support. We are
grateful to the EPSRC (AMB) and Prof. Simon Redfern and the
Department of Earth Sciences and the University of Cambridge
for general support (GIL). We are grateful to Prof Jeremy K. M.
Sanders and Prof. Jack Harrowfield for important discussions on
this topic (ARS).
2
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Chemistry - A European Journal
10.1002/chem.201801740
COMMUNICATION
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COMMUNICATION
The new, catalyst free, method were
Szymon Sobczak, Wojciech Drożdż,
Giulio I. Lampronti, Ana M. Belenguer ,
Andrzej Katrusiak *, Artur R.
Stefankiewicz *
applied
for
effective
disulfide
metathesis. Utilization of combined
pressure and temperature stimuli,
allowed to obtain low-density crystal
structure of heterodimeric-disulfide
product.
Page No. – Page No.
Dynamic Covalent Chemistry under
High-pressure: a New Route to
Disulfide Metathesis
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