Tackling poison and leach: Catalysis by dangling thiol-palladium functions within a porous metal-organic solid

Article abstract of DOI:10.1039/c5cc00140d

Self-standing thiol (-SH) groups within a Zr(iv)-based metal-organic framework (MOF) anchor Pd(ii) atoms for catalytic applications: the spatial constraint prevents the thiol groups from sealing off/poisoning the Pd(ii) center, while the strong Pd-S bond precludes Pd leaching, enabling multiple cycles of heterogeneous catalysis to be executed. This journal is

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Tackling Poison and Leach: Catalysis by Dangling
Thiol-Palladium Functions within a Porous Metal-
Organic Solid
Cite this: DOI: 10.1039/x0xx00000x
†
a
†b
b
b
c
Received 00th January 201x,
Accepted 00th January 201x
Bo Gui,a KaꢀKit Yee, YanꢀLung Wong, ShekꢀMan Yiu, Matthias Zeller, Cheng
b
Wang,* and Zhengta Xu*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Self-standing thiol (-SH) groups within a Zr(IV)-based the widely used SMRs for CꢀC bond formation between aryl
5
groups. Such poisoning can be ascribed to the strong and intractable
metal-organic framework (MOF) anchor Pd(II) atoms for
catalytic applications: the spatial constraint prevents the
thiol groups from sealing off/poisoning the Pd(II) center,
while the strong Pd-S bond precludes Pd leaching, enabling
multiple cycles of heterogeneous catalysis to be executed.
thiolꢀPd interactions that effectively seal off the coordination sphere
In traditional solution chemistry, the steric effect is commonly
exerted via bulky substituents, as is often practiced by coordinating
bulky ligands around metal centers. Such bulky ligands block off the
coordination sphere, kinetically stabilize the coordinatively
unsaturated metal centers, and often give rise to remarkable
1
reactivities such as CꢀH bond and N activation. Here we depart
2
from the dynamic, freeꢀflowing solution regime, and set out instead
to explore the steric effect in the context of organized open
2
frameworks in the solid state (e.g., MOF systems ). For this, we
envision, within a porous solid state network, a dangling, relatively
isolated donor site that is without immediate neighboring donors; the
incoming metal guest would perforce be bonded to at most one
donor from the host net (the other donors being too far away). The
metal center thus affixed to the dangling, isolated donor, would take
on a distinct unsaturated character in its coordination sphere, with
Fig. 1 Synthetic scheme for the ZrDMTD network. The network is
simplified as an octahedral cage taken from the single crystal structure.
The dotted line indicates a shortest intermolecular distance of 5.24 Å
between sulfur atoms. Disorder of the central benzene ring is shown in
only one linker; Zr coordination polyhedra displayed in green.
3
open sites to accommodate substrates, and to effect catalytic
processes not feasible under solution conditions. We here
demonstrate that the dangling effect converts thiols from catalyst
poisons into effective anchors for palladium atoms, resulting in
highly recyclable heterogeneous catalysis for carbonꢀcarbon bond
formation reactions (the Suzuki–Miyaura reaction, SMR). Such a
and suppress the bonding lability that is crucial for the catalytic
process. Specifically, in a solution environment where the thiol
groups can freely approach the metal center, palladium(II) dithiolate
4
study thus complements the ongoing advances in MOF catalysis,
species—e.g., Pd(SR) —readily form as a thermodynamic trap from
where intentions to exploit reactivity arising from the dangling,
isolated character of the donors are less distinct.
The thiol donor is well suited for highlighting the dangling effect,
as thiols in the solution phase are known to be incompatible with
many transition metal catalysts (especially the heavy members of Pd
and Pt). For example, thiol groups readily poison the Pd catalyst for
2
which reactivation into the catalytic cycle often entails elaborately
6
designed ligands (e.g., the Josiphos ligands ).
By contrast, such poisoning from the thiol donors could be
prevented in the setting of a rigid framework where the thiol groups
are spaced too far apart to fully bond around the Pd center—the
sulfur atoms therefore would not block off the catalytic steps as in
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the solution case. Moreover, the use of the dangling, isolated thiol pore region. Unless otherwise mentioned, the ZrDMTD crystals used
groups to anchor Pd atoms effectively turns the intractable PdꢀS in the following studies were continuously covered by solvents.
bond on its head, as its very strength would help to suppress Pd
leaching, and to create more durable heterogeneous catalysts.
Upon contact with an acetonitrile solution of Pd(CH CN) Cl ,
3 2 2
the ZrDMTD crystals turned from light yellow to red (Fig. S5), with
In general, leaching remains a central problem in heterogeneous the resultant Pdꢀloaded sample (ZrDMTDꢀPd) exhibiting a distinct
−1
catalysis. Instead of being truly “heterogeneous”, many supported Pd Raman peak around 386 cm (Fig. S2) that corresponds to the PdꢀS
catalysts for CꢀC coupling (e.g., SMR and Heck) reactions actually stretch. The Pd uptake is quantified by ICP elemental analysis,
7
opearate through leached soluble Pd species.
To verify the which indicated a Zr/Pd ratio of 1:0.70 (corresponding to a 2.9:1
heterogeneous nature, more rigorous procedures like the threeꢀphase S/Pd ratio). The strong and sharp PXRD peaks (Fig. 2, pattern d) of
7e, 7f, 8
test are needed.
For example, with the three phases consisting the ZrDMTDꢀPd sample also indicated retention of the structural
of the catalyst solid, the solution phase, and a separate solid phase integrity of the host net.
anchoring a test reagent (e.g., an aryl bromide for SMR), a truly
The catalytic activity of the ZrDMTDꢀPd crystals was examined
heterogeneous catalyst, without leaching, should not cause under especially convenient conditions for the SMR: by simply
significant reaction of the test reagent anchored on the separate solid heating the reactants and the crystals (Pd/substrate molar ratio: about
phase.
Our choice of the framework system in which to install the
1%) and in ethanolꢀꢀwithout the commonly required phosphine
dangling thiol groups is facilitated by recent discoveries of robust
frameworks based on carboxylate linkers and chemically very hard
9
10
11
Al(III), Cr(III) and Zr(IV) ions. For example, hard ions generally
prefer to bond with the carboxyl group (e.g., over the soft thiol), and
freeꢀstanding thiol functions can be appended to the crystalline host
12
net, as demonstrated in an earlier Eu(III) system back in 2009, and
in the recent Zr(IV) networks (e.g., from terephthalateꢀbased
13,14
linkers).
To explore the dangling effect, we here use the
elongated building block of DMTD (DM: dimercapto; TD:
terphenyldicarboxyl; Fig. 1), in order to make for larger pore
opening, and to facilitate the diffusion of substrates. The longer
molecule of DMTD, with the thiol groups being positioned at its
central ring, also serve to further space apart the thiol groups, so as
to accentuate their dangling, solitary character.
Fig. 2 PXRD patterns: (a) calculated from the singleꢀcrystal structure of
ZrDMTD; (b) asꢀmade ZrDMTD; (c) asꢀmade ZrDMTD placed in air for
Reaction of H DMTD and ZrCl (see SI) yielded single crystals
2
4
1
0 mins; (d) ZrDMTDꢀPd; (e) the sample of (d) after 8 cycles of catalytic
of the framework ZrDMTD [composition: Zr O (OH) (DMTD) ; see
6
4
4
6
reaction; and (f) the sample of (e) after being placed in air for 2 days.
Patterns a, b, d and e were taken with crystals covered by a thin layer of
DMF to prevent solvent loss.
SI for more details, e.g., Fig. S1ꢀ3 for the TGA plot, Raman and IR
spectra], which features the UiOꢀ68 topology, with DMTD being the
linear strut and Zr O (OH) clusters the 12ꢀconnected nodes (Fig.
6
4
4
1
5
1
). The freeꢀstanding thiol group in the crystal structure is ligands, and without the need to exclude air. Even without stirring,
disordered over four sets of symmetryꢀrelated positions, from which the reactions proceed smoothly for iodide substrates, generally
the shortest S···S distance across the DMTD linkers is found to be completing within several hours, with yields of the isolated
5
.24 Å (Fig. 1). Such farꢀapart S atoms are not disposed to be productsꢀꢀin spite of the small reaction scale—being above 80%
simultaneously bonded with the same metal center, e.g., a typical Pdꢀ (Tables 1 and S1). For bromobenzene and the activated derivatives
S bond is of 2.20 Å, which would dictate the other PdꢀS distance to (e.g., by –F or –CN), similar yields can also be achieved, with
be longer than 3.00 Å. In other words, only one S atom from the host somewhat longer reaction times (e.g., 12 hrs). Aryl bromides with
grid could fully bond with each individual Pd center, thus leaving electronꢀdonating groups, are, however, less reactive under similar
open its coordination sphere.
conditions (e.g., Table S1, entries 9 and 10). Higher efficiencies,
The ZrDMTD crystals can be safely stored in organic solvents however, can be achieved by magnetic stirring—e.g., within one
(
e.g., EtOH, CHCl and DMF) for months, with no degradation of hour, an iodo substrate generally registers a conversion rate over
3
crystallinity (e.g., as checked by powder Xꢀray diffraction, PXRD). 90% as indicated by solution NMR (see Fig. S8 for details).
However, when the crystals are taken out of the solvent, the PXRD During the catalytic reaction, the red crystals of ZrDMTDꢀPd
pattern starts to degrade within minutes, resulting in two broad peaks turned black, suggesting the formation of Pd(0) species. XPS study
at the lowerꢀangle region (Fig. 2, pattern c). The degraded structural on the Pd 3d5/2 state is also revealing. Before catalysis, the (red)
order is also reflected in the gas sorption properties. Unlike most ZrDMTDꢀPd sample exhibits one single peak at 337.7 eV,
other Zrꢀbased MOF solids, the desolvated ZrDMTD sample associated with Pd(II) species. After catalysis, the blackened sample
exhibits no significant N sorption at 77 K. Nevertheless, at 273 K, exhibits two peaks: one remaining at 337.7 eV, and the other being a
2
−3
CO sorption does take place (pressure range: from 8 × 10 to 780 new, strong peak at the lower energy of 335.4 eV, which is
2
mmHg) with reproducible isotherms (Fig. S4) indicating a BET consistent with the lower binding energy of Pd(0) species (Fig. S6).
2
surface area of 1361 m /g. Such different sorption behaviors toward On the other hand, the regular octahedral shape of the crystals was
N and CO are often seen in porous polymers, wherein the pores maintained (see Fig. S7 for SEM images), and the structural integrity
2
2
blocked at 77 K become more accessible (e.g., to CO gas) at higher of the crystalline host net was confirmed by powder Xꢀray
2
6
1
temperatures due to stronger thermal motions. As for the diffraction, which reveals the same sharp peaks as the asꢀmade
desolvated solid of ZrDMTD, the PXRD and BET studies together sample (Fig. 2, pattern e). Notably, no peaks corresponding to
point to a largely disordered network with restricted access to the elemental Pd were observed in the PXRD pattern, indicating that the
2
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individual Pd(0) atoms are likely to remain well dispersed on within Moreover, even when a large amount of the unmetallated ZrDMTD
the host frameworkꢀꢀi.e., the Pd atoms do not aggregate to form crystals (i.e., containing free thiols groups in the pores)are added to
sizable, diffracting nanoparticles.
the reaction (i.e., as a form of poison test), no significant impairment
on the ZrDMTDꢀPd catalyst was observed, e.g., with the iodo
substrate all consumed within 1.5 hrs (Fig. S11). Altogether, the
leaching of Pd species was found to be negligible. Future
deployment of the ZrDMTDꢀPd solid in a continuous flow setup
would serve to boost its overall turnover numbers, and highlight its
operational advantages as a heterogeneous catalyst.
Table. 1 Efficiencies of selected SuzukiꢀMiyaura reactions catalyzed by
ZrDMTDꢀPd crystals and control experiments
[a]
As a comparative study to highlight the catalytic activity arising
from the spatial confinement effect imposed by the porous
framework (in the form of the dangling –SH groups), the free ligand
of H DMTD was used in conjunction with PdCl (CH CN) (similar
reaction conditions, with a similar ligand/Pd ratio as in the
ZrDMTDꢀPd solid, see SI for details) for the SMR. Very little
Time Isolated Yield
[
e]
Entry
X
Catalyst
TON
(hr)
(%)
2
2
3
2
[f]
1
2
3
4
5
6
7
8
9
I
I
None
5
ND
0
ZrDMTDꢀPd
cycle 1
5
5
86.0
83.1
82.0
126
122
120
catalytic activity was observed with the free ligand H DMTD: for
2
ZrDMTDꢀPd
the iodo substrate (Table 1, entry 6), the yield is below 10%, while
bromobenzene remains unreacted even after being heated for 12 hrs
(Table 1, entry 9).
I
[b]
cycle 2
ZrDMTDꢀPd
I
5
[b]
cycle 3
ZrDMTDꢀPd
To further illustrate that the catalytic Pd species are operating
[d]
[d]
I
5
84.3
124
[
b]
cycles 4ꢀ8
[
c]
I
H
2
DMTD/PdCl
2
5
8.6
13
47
125
0
Degraded
I
5
32.4
85.6
[
g]
ZrDMTDꢀPdꢀd
ZrDMTDꢀPd
Br
Br
12
12
[c]
[f]
H
2
DMTD/PdCl
2
ND
[
a] Additional test reactions and the procedures included in SI. [b] See SI for the
cycling procedure. [c] With a molar ratio of 1:0.70 between DMTD and
PdCl (CH CN) . [d] Average value of five runs. [e] TON defined as the molar ratio
H
2
2
3
2
between product and Pd. [f] Not detected from TLC monitoring. [g] Degraded by
exposing ZrDMTDꢀPd to air (PXRD pattern shown in Fig. 2f).
Aggregation of the Pd(0) species, however, does occur when,
after the catalytic cycle, the black ZrDMTDꢀPd crystals were placed
in air (i.e., without the covering solvent). Like the aboveꢀmentioned
ZrDMTD crystals, the PXRD peaks from the host net broaden
significantly. Simultaneously, new, broad peaks at higher angles
appeared (pattern f of Fig. 2), which can be ascribed to crystalline Pd
particles (i.e., 2θ 39.96◦ and 46.58◦, corresponding to the 111 and
Fig. 3 A schematic of the ZrDMTDꢀPdꢀcatalyzed coupling reaction
between a boronic acid and 4ꢀbromoꢀ2ꢀfluorobenzonitrile (bfbn) in the
presence of the bulky substrate M; the lack of reaction of M indicates
the heterogeneous nature of the solid catalyst of ZrDMTDꢀPd (shown as
an octahedral cage).
within the pores of the host net, we prepared molecule M (Fig. 3) as
a bulky substrate of the SMR. In contrast with the above mentioned,
smaller substrates which readily enter into the pores of ZrDMTD
2
00 diffractions from the Pd lattice). The degraded ZrDMTDꢀPd
(
pore opening: ~9 Å), molecule M, with a crossꢀsection above 12 Å,
solid (with the Pd atoms aggregated to form particles) shows largely
subdued catalytic activity: for example, even for an iodo substrate
is too bulky to penetrate the host net. In the setting of the threeꢀphase
test (mentioned above) for verifying the heterogeneous nature of the
catalytic process, molecule M can therefore be used to serve the
purpose of the third phase (the other two being the liquid solution
and the MOF catalyst). In our test, molecule M and the small
substrate 4ꢀbromoꢀ2ꢀfluorobenzonitrile (bfbn) were added together
to a reaction mixture containing the boronic acid reactant, the
(
(
entry 7, Table 1), the isolated yield was found to be only 32%
TON: 47), less than half the yield obtained from the crystalline
ZrDMTDꢀPd catalyst. The subdued catalytic activity can be ascribed,
in part, to the reduced accessibility of the Pd atoms after they pile up
to form the nanoparticles.
Back to the crystalline ZrDMTDꢀPd (containing more dispersed
Pd species): the recyclability of this solid catalyst is highlighted in
the constant yields and TONs observed in the 8 cycles tested: no
trend of catalytic activity loss was observed, and the crystallinity of
the host framework remained intact (as seen in PXRD pattern e, Fig.
ZrDMTDꢀPd catalyst solid and the solvents of EtOH/Et N. While
3
the small bfbn molecule readily reacted to give the expected product,
no reaction of M was observed (e.g., as monitored by TLC; see Fig.
S12). Moreover, the more reactive iodo version of M also exhibited
no reaction in a similar test (Fig. S13). Such observations strongly
support the heterogeneous nature of the ZrDMTDꢀPd catalyst.
To sum up, the catalytic activity observed of the ZrDMTDꢀPd
crystals, in contrast with the negative controls of the free ligand
H DMTD/Pd(II) system and the bulky molecule M, highlights the
dangling effect imposed by the porous host net, which turns the
normally poisonous thiol groups into effective ligands as well as
2
). To further keep track of the Pd species, the supernatant was
subjected to ICPꢀOES analysis (see SI) and this registered no Pd
presence; correspondingly, the Pd content in the crystals after the 8
catalytic cycles remained unchanged (see SI for details). Also, the
isolated supernatant exhibits no catalytic activity under similar
reaction conditions (as shown by the NMR data in Fig. S9); and a
hot filtration test revealed no further reaction in the filtrate (Fig. S10).
2
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as to uncover novel reactivities within MOFs and other porous media
1
7
(e.g., porous organic frameworks and cages).
This work was supported by City University of Hong Kong
Project 9667092), the Research Grants Council of HKSAR (GRF
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(
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Notes and references
*
Corresponding author
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†
a
These authors contributed equally to this work.
Key Laboratory of Biomedical Polymers (Ministry of Education),
College of Chemistry and Molecular Sciences, Wuhan University,
Wuhan 430072, China. Eꢀmail: chengwang@whu.edu.cn
b
Department of Biology and Chemistry, City University of Hong Kong
8
3 Tat Chee Avenue, Kowloon, Hong Kong, China. Eꢀmail:
zhengtao@cityu.edu.hk.
c
Department of Chemistry, Youngstown State University, One
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