Mapping-Out Catalytic Processes in a Metal–Organic Framework with Single-Crystal X-ray Crystallography

Article abstract of DOI:10.1002/anie.201611254

Single-crystal X-ray crystallography is employed to characterize the reaction species of a full catalytic carbonylation cycle within a Mn^II-based metal–organic framework (MOF) material. The structural insights explain why the Rh metalated MOF is catalytically competent toward the carbonylation of MeBr but only affords stoichiometric turn-over in the case of MeI. This work highlights the capability of MOFs to act as platform materials for studying single-site catalysis in heterogeneous systems.

Full text of DOI:10.1002/anie.201611254

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Communications
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International Edition: DOI: 10.1002/anie.201611254
German Edition: DOI: 10.1002/ange.201611254
Catalysis in MOFs
Hot Paper
Mapping-Out Catalytic Processes in a Metal–Organic Framework with
Single-Crystal X-ray Crystallography
Alexandre Burgun, Campbell J. Coghlan, David M. Huang, Wenqian Chen, Satoshi Horike,
Susumu Kitagawa, Jason F. Alvino, Gregory F. Metha, Christopher J. Sumby,* and
Christian J. Doonan*
Abstract: Single-crystal X-ray crystallography is employed to
characterize the reaction species of a full catalytic carbon-
ylation cycle within a MnII-based metal–organic framework
(MOF) material. The structural insights explain why the Rh
metalated MOF is catalytically competent toward the carbon-
ylation of MeBr but only affords stoichiometric turn-over in
the case of MeI. This work highlights the capability of MOFs to
act as platform materials for studying single-site catalysis in
heterogeneous systems.
chemical transformations in a stable MOF can be elucidated
via SCXRD analysis under relatively demanding condi-
tions.[10] These advances in structural characterization are
noteworthy as SCXRD studies have proven to be an essential
technique for understanding structure-function relationships
for molecular species.[11] Accordingly, the application of
SCXRD to examining the products of reactions carried out
within MOF pores will offer unique insight into the chemistry
of this bespoke reaction environment.
Herein we carry out the carbonylation of MeBr in a single
MOF crystal and, remarkably, demonstrate that SCXRD can
be used to elucidate the intermediates and products of
a complete reaction cycle (Scheme 1). This chemistry is of
significant interest as carbonylation of the analogous halo-
alkane CH3I is a critical step in the commercial production of
acetic acid, a process that represents one of the major
industrial applications of homogeneous catalysis.[12] Our
results highlight that MOFs are an excellent platform for
providing structural insight into chemical reactivity within
porous solids and are therefore key materials for guiding the
design and development of novel catalysts.
We have previously reported post-synthetic metalation
chemistry of the MnII-based MOF 1 (1 = [Mn3(L)2(L’)],
where LH2 = bis(4-(4-carboxyphenyl)-1H-3,5-dimethylpyra-
zolyl)methane; L’ possesses a bis(3,5-dimethylpyrazol-1-
yl)methane moiety that remains non-coordinated in the as-
synthesized MOF.[6a] The flexible bis-pyrazole chelating group
that lines the pores of 1 can be quantitatively metalated, thus
facilitating examination of post-synthetically metalated ana-
logues by SCXRD methods. A remarkable observation was
that a RhI metalated species, 1·[Rh(CO)2][Rh(CO)2Cl2],
retained single crystallinity after the consecutive oxidative
addition and methyl migration steps that resulted from
exposure to CH3I. Indeed this robustness allowed for
structural characterization of the octahedral product 1·[Rh-
(CO)(CH3CN)(COMe)I]I. Based on the chemistry of struc-
turally analogous molecular RhIII species, we hypothesized
that 1·[Rh(CO)(CH3CN)(COMe)I]I could be induced to
reductively eliminate acetyl iodide (ICOMe) and complete
the carbonylation reaction cycle within 1. However, 1·[Rh-
(CO)(CH3CN)(COMe)I]I proved unusually stable and cou-
pled thermogravimetric analysis-mass spectrometry (TGA-
MS) experiments confirmed that conditions above 1508C
were required to eliminate an acetyl moiety (Figure SI1).[13]
Close inspection of the crystal structure of 1·[Rh(CO)-
(CH3CN)(COMe)I]I indicates that the geometric rearrange-
ment required for reductive elimination, which would bring
acetyl and iodo ligands into a cis arrangement,[14] is sterically
M
etal–organic frameworks (MOFs) are a class of porous
materials that typically exhibit crystalline structures.[1] This
salient property has facilitated a number of detailed X-ray
and neutron diffraction studies that have provided funda-
mental structural information with respect to gas adsorption
processes,[2] the coordination environment of post-syntheti-
cally added metal ions,[3] the structure of stabilized reactive
moieties,[4] framework flexibility,[5] and chemical transforma-
tions within pore networks.[6] Furthermore, the periodic
architectures of selected MOFs have been employed as
matrices for occluding and ordering guest molecules to
facilitate examination by single-crystal X-ray diffraction
(SCXRD).[7] The aforementioned studies have contributed
to uncovering new and significant insights into the chemistry
and physical properties of porous materials and their guests,
and serve to highlight the importance and continued interest
in MOFs.
Though the benefits of crystallinity are clear, early
examples of MOF materials were considered structurally
fragile and retention of crystallinity generally required careful
handling procedures.[8] This limitation has now been over-
come and many examples of chemically robust MOF struc-
tures have been reported.[9] Indeed, we and others have
recently shown that single-crystal to single-crystal (SC-SC)
[*] Dr. A. Burgun, Dr. C. J. Coghlan, Dr. D. M. Huang, Dr. J. F. Alvino,
Prof. G. F. Metha, Prof. C. J. Sumby, Prof. C. J. Doonan
Department of Chemistry and Centre for Advanced Nanomaterials
The University of Adelaide
Adelaide, South Australia 5005 (Australia)
E-mail: christopher.sumby@adelaide.edu.au
christian.doonan@adelaide.edu.au
Dr. W. Chen, Dr. S. Horike, Prof. S. Kitagawa
Department of Synthetic Chemistry and Biological Chemistry,
Graduate School of Engineering, and Institute for Integrated Cell-
Materials Science (iCeMS), Kyoto University
Kyoto (Japan)
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.201611254.
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Compared with the reaction product obtained
from CH3I, two salient structural differences are
observed in the single-crystal structure (Figure 2).
First, the equatorial plane comprises two N donors
from 1 and two solvent molecules (CH3CN). In
contrast, reaction with CH3I affords an equatorial
plane consisting of two N donors, one solvent
molecule (CH3CN) and one CO (the solvent
ligand and the CO are disordered). The second
difference is with respect to the distribution of the
axial donors. For the CH3I reaction product, the
iodo and acetyl ligands are disordered, with an
approximate 50% site occupancy over the two
axial sites, whereas for 1·[Rh(CH3CN)2-
(COMe)Br]Br the Br and the acetyl ligands fully
occupy their respective positions (Figure 2b).
These differences may be attributed to the
reduced size of the bromo ligand compared with
iodide. Indeed, in the commonly proposed reduc-
tive elimination process, the trans COMe and
halide ligands isomerize to a less energetically
stable cis arrangement prior to the elimination of
acetyl halide (XCOMe).[15,18] This geometric rear-
rangement is evidently unfavorable for the iodo
species, which does not readily reductively elimi-
Scheme 1. Catalytic cycle of the carbonylation of MeX (X=I, Br) catalyzed by
1·[Rh(CO)2]Br (R=the remainder of the MOF backbone, O.A.=oxidative addition,
Ins=1,1-migratory insertion, R.E.=reductive elimination). The proposed catalytic
cycle under solution-phase conditions is shown in black and under gas-phase
conditions is shown in red.
demanding.[15] Accordingly, we explored the analogous
chemistry of 1 with the smaller and less-reactive alkyl halide
CH3Br.
nate ICOMe, but is permitted for the Br analogue, which,
according to the structure of the reaction product (see below),
undergoes reductive elimination of BrCOMe and then
a further oxidative addition and migratory insertion to
consume both CO ligands (Scheme 1).
Crystals of 1·[Rh(CO)2][Rh(CO)2Cl2] were exposed to
CH3Br vapor in dry acetonitrile (CH3CN) for 11 days, and
then washed with fresh CH3CN (ꢀ 6) prior to examination by
SCXRD. Analysis of the X-ray data confirmed that 1·[Rh-
(CO)2][Rh(CO)2Cl2] had transformed to an octahedral RhIII
species, 1·[Rh(CH3CN)2(COMe)Br]Br (Figure 1); the pres-
ence of a BrÀ in the structure suggests that the RhI anion of
the starting material had also reacted with MeBr and was
expelled from the MOF. The product formulation was
supported by IR spectroscopy, which shows stretches charac-
teristic of coordinated CH3CN molecules[16] at 2320 and
2300 cmÀ1 and a Rh-bound acetyl group[17] at 1726 cmÀ1 in the
spectra of 1·[Rh(CH3CN)2(COMe)Br]Br (see Figure 3). Fur-
thermore, no peaks are observed between 1990 and
2100 cmÀ1, supporting the reaction of the carbonyl ligands.
Typically, the oxidative addition of alkyl halides to
a transition-metal complex proceeds via an SN2 reaction
mechanism.[14] Thus, in the case of the MOF (which is
asymmetric about the equatorial plane of the Rh center), if
the substrate does not preferentially approach one side of the
1·[Rh(CO)2]+ plane it is expected that the oxidatively added
axial ligands of the RhIII product would be uniformly
distributed with 50% occupancy. Indeed this is observed for
1·[Rh(CO)(CH3CN)(COMe)I]I, which furthermore does not
appear to allow facile rearrangement after formation. How-
ever, for the structure of the Br analogue 1·[Rh(CH3CN)2-
(COMe)Br]Br, the axial Br and COMe ligands refine with full
occupancies. We posit that this is due to the reduced size of
Figure 1. Reaction scheme showing the X-ray crystal structures of a catalytic intermediate and reaction product of the methyl bromide
carbonylation cycle within MOF 1. All representations are shown along the a axis with views of a) the starting material 1·[Rh(CO)2][Rh(CO)2Cl2];
b) an intermediate 1·[Rh(CH3CN)2(COMe)Br]Br; and c) the reaction product 1·[Rh(CO)2]Br. The MOF backbone is shown in blue with a transparent
van der Waal’s surface; C black; N dark blue; O red; Rh orange, Cl yellow; Br green).
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Figure 2. Fobs electron-density maps and corresponding crystal-structure fragments for a) 1·[Rh(CH3CN)2(COMe)Br]Br, top view showing that both
CH3CN ligands are fully occupied and b) side view showing that the axial Br (green) and COMe ligands are fully occupied. c) 1·[Rh(CO)(CH3CN)-
(COMe)I]I top view showing that the CH3CN and CO ligands are disordered over both equatorial positions and d) side view showing that the axial
I (purple) and COMe ligands are disordered with approximately 50% site occupancy.
the Br ligand allowing structural rearrangement of the ligands
to an energetically preferred position and necessarily requires
the formation of a cis arrangement of the groups as a prelude
to reductive elimination. In the present case the Rh complex
is anchored to the MOF backbone and is enshrouded by
a sterically and electronically anisotropic environment. Thus
it can be anticipated that the positions adopted by -Br and
-COMe ligands will correspond to the global energy mini-
mum. To verify this we performed density functional theory
calculations to determine the relative stability of the two
alternative structures of 1·[Rh(CH3CN)2(COMe)Br]Br that
differ by the axial positions of the Br and COMe ligands. The
calculations were carried out on a simplified model of the Rh
complex using the same methodology applied in our previous
work,[6a] and reveal that the experimentally observed struc-
ture is almost 19 kJmolÀ1 more stable than the alternative
structure (see Supporting Information for calculation details).
Exploring the potential of MOFs as heterogeneous
catalysts is a burgeoning field as the “building-block”
approach to their synthesis offers precise control of pore
size and functionality.[19] Furthermore, it allows for the
introduction of known homogeneous catalyst moieties into
a heterogeneous environment.[20] Accordingly, we sought to
structurally elucidate the reaction products of the full
carbonylation cycle of CH3Br within MOF 1. In the inter-
mediate 1·[Rh(CH3CN)2(COMe)Br]Br (Figure 2a), each of
the available equatorial positions is occupied by solvent
molecules, indicating that both CO molecules of the starting
complex 1·[Rh(CO)2][Rh(CO)2Cl2] have been consumed. For
the reaction cycle to proceed, additional equivalents of CO
are required at the Rh site. Despite carrying out the reaction
under elevated pressures of CO (10–14 bar) and temperatures
(40–808C) in solution (acetonitrile or THF), 1·[Rh(CH3CN)2-
(COMe)Br]Br was the only reaction product identified by X-
ray and IR analysis. This result is not unexpected given that
a presumably low concentration of dissolved CO must diffuse
through the reaction solution and into the pore network of the
MOF to reach the Rh active site. Therefore, to complete the
carbonylation cycle we exposed dried crystals of 1·[Rh-
(CH3CN)2(COMe)Br]Br to 12 bar of CO at 808C for 24 h.
Analysis of SCXRD data indicated that octahedral 1·[Rh-
(CH3CN)2(COMe)Br]Br had transformed to the square-
planar RhI complex 1·[Rh(CO)2]Br (Figure 1c), thus con-
firming that the addition of CO had promoted the reductive
elimination of BrCOMe. As expected, the RhI center adopts
a square-planar geometry coordinated to both N pyrazole
donors from 1 and two CO ligands, with the BrÀ anion located
within the pores. It is noteworthy that the X-ray crystal
structure of 1·[Rh(CO)2]Br shows no clear evidence of
defined electron density in the axial positions, indicating
that the reductive elimination of acetyl bromide is fully
complete. Additionally, the cationic bis-carbonyl RhI species
proposed by X-ray analysis was confirmed by IR spectrosco-
py, which shows four characteristic CO stretches at 2099, 2066,
2041 and 1991 cmÀ1 (Figure 3) and no Rh-bound acetyl
stretch at 1726 cmÀ1. However, the IR spectrum does display
a carbonyl stretch at 1694 cmÀ1 that can be attributed to the
=
C O stretch of an acetyl unit. This suggests that the product
of the reductive elimination step remains within the MOF
pores. Thus, SCXRD studies established that the catalytic
carbonylation of CH3Br did not proceed in solution but that
a single cycle could be completed in the gas phase. Inspired by
this finding, we investigated the catalytic performance of
1·[Rh(CO)2]Br in the gas phase.
Catalysis experiments were performed in a pressurized,
stainless steel cell and the reaction was continuously moni-
tored by sampling a small amount of the gas head-space in
a residual gas analyzer (see Supporting Information for a full
description). Crystals of pre-catalyst 1·[Rh(CH3CN)2-
(COMe)Br]Br (5 mmol) were loaded into the cell and, after
evacuating the system for 1 h, 10 bar of a 1:9 MeBr/CO gas
mixture was introduced. The reaction cell was left at room
temperature for 40 min, then heated at 808C for 40 min and at
1208C for 9 h. Upon heating under the pressurized MeBr/CO
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unexpected and can be attributed to the kinetics of the rate-
determining MeX oxidative addition step[18,22] which is much
slower for MeBr than for its MeI counterpart[23] (for example,
the reaction of 1·[Rh(CO)2][Rh(CO)2Cl2] with MeX is
completed after 2 days at room temperature for X = I,
whereas it is completed after 3 days at 408C and 7 days at
room temperature for the X = Br reaction). This is related to
the Me-X bond dissociation energies: 293 kJmolÀ1 for Me-Br
and 235 kJmolÀ1 for Me-I.[24]
Metal–organic frameworks show excellent promise as
platform materials for heterogeneous catalysis. Their unique
chemistry offers the precise control of single-site catalysis
characteristic to homogeneous systems[25] while obviating
issues, such as catalyst aggregation, that typically lead to
deactivation. Herein we have shown that the intrinsic
crystallinity of MOFs facilitates the use of SCXRD studies
to elucidate the reaction products of a full carbonylation
cycle, and furthermore, to understand the observed and
different reactivity of methyl halides. Such detailed structural
insights have underpinned advances in homogeneous systems
and will undoubtedly guide fine-tuning of MOFs catalysts.
Indeed our work shows that in addition to framework pore
dimensions the steric environment of the catalytically active
site must be carefully considered. Also framework flexibility
is desired as this facilitates changes in geometry at the
reaction site without applying strain on the links. In summary,
the present work serves to highlight how the robust and highly
ordered structures of MOFs can be excellent platforms for
studying chemical reactivity in porous solids.
Figure 3. Infrared spectra of 1·[Rh(CO)2][Rh(CO)2Cl2] (black), 1·[Rh-
(CH3CN)2(COMe)Br]Br (red), and 1·[Rh(CO)2]Br (blue). IR stretches:
a) coordinated CH3CN, b) free CH3CN, g) coordinated CO, d) coordi-
nated acetyl, and e) free acetyl product.
atmosphere, active catalyst 1·[Rh(CO)2]Br was generated
in situ (Figure SI8). Real-time analysis of the gas-phase
reaction cell by mass spectrometry confirmed the presence
of peaks attributable to [OCMe]+ (i.e. m/z 43), with slow
product generation at 808C, followed by a rapid ejection of
product from the MOF pores upon heating to 1208C, and then
sustained production for 8 h (Figure 4). Furthermore, upon
terminating the reaction the presence of acetyl bromide in the
reaction mixture and within the MOF material was also
confirmed by gas chromatography and energy dispersive X-
ray analyses, respectively (Figure SI10, SI11 and Table SI3).
After 10 h of catalysis, 56 mmol (= 61À5, with 5 mmol from the
pre-catalyst) of acetyl bromide had been produced, indicating
that approximately 11 catalytic cycles had been achieved.
PXRD analysis indicated that the MOF catalyst retains
crystallinity under these conditions (Figure SI7) and, further,
no evidence of Rh or Rh oxide nanoparticles were
observed.[21] The slow production rate of our system is not
Acknowledgements
C.J.D., C.J.S., and D.M.H. gratefully acknowledge the Aus-
tralian Research Council for funding (DP160103234). C.J.D.
would like to thank the JSPS/AAS for a visiting professorial
fellowship. Aspects of this research were undertaken on the
MX1 and MX2 beamlines at the Australian Synchrotron,
Victoria, Australia. D.M.H. gratefully acknowledges compu-
tational resources provided by the Australian Government
through the National Computing Infrastructure under the
National Computational Merit Allocation Scheme.
Conflict of interest
The authors declare no conflict of interest.
Keywords: carbonylation · heterogeneous catalysis · MOFs ·
rhodium complexes · structure elucidation
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Manuscript received: November 17, 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
Catalysis in MOFs
Crystallization not needed. A MnII-based
MOF is used as a matrix to isolate and
structurally elucidate the chemistry of
a single-site rhodium(I) catalyst that
carries out the carbonylation of methyl
halides. X-ray crystal structures of cata-
lytic intermediates were obtained and
explain why carbonylation occurs with
MeBr but not MeI.
A. Burgun, C. J. Coghlan, D. M. Huang,
W. Chen, S. Horike, S. Kitagawa,
J. F. Alvino, G. F. Metha, C. J. Sumby,*
C. J. Doonan*
&&&& — &&&&
Mapping-Out Catalytic Processes in
a Metal–Organic Framework with Single-
Crystal X-ray Crystallography
6
www.angewandte.org
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
These are not the final page numbers!