Activation of Methyltrioxorhenium for Olefin Metathesis in a Zirconium-Based Metal-Organic Framework

Article abstract of DOI:10.1021/jacs.8b02837

The zirconium nodes of the metal-organic framework (MOF) known as NU-1000 serve as competent supports for the activation of methyltrioxorhenium (MTO) toward olefin metathesis. Itself inactive for olefin metathesis, MTO becomes an active catalyst only when immobilized on the strongly acidic Lewis acid sites of dehydrated NU-1000. Uptake of MTO at the dehydrated secondary building units (SBUs) occurs rapidly and quantitatively to produce a catalyst active in both gas- and liquid-phase processes. These results demonstrate for the first time the utility of MOF SBUs for olefin metathesis, an academically and industrially relevant transformation.

Full text of DOI:10.1021/jacs.8b02837

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Article
Activation of Methyltrioxorhenium for Olefin Metathesis
in a Zirconium-Based Metal-Organic Framework
Maciej D. Korzynski, Daniel F. Consoli, Shiran Zhang, Yuriy Roman-Leshkov, and Mircea Dinca
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 07 May 2018
Downloaded from http://pubs.acs.org on May 7, 2018
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Activation of Methyltrioxorhenium for Olefin Metathesis in a Zirco-
nium-Based Metal-Organic Framework
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Maciej D. Korzyński, Daniel F. Consoli, Shiran Zhang, Yuriy RománꢀLeshkov* and Mircea
,
†
Dincă*
†
‡
Department of Chemistry and Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, United States
Supporting Information Placeholder
temperatures and are less tolerant of functionalized olefins. Imꢀ
portant milestones in rhenium oxide chemistry were the discovꢀ
ABSTRACT: The zirconium nodes of the metalꢀorganic frameꢀ
work (MOF) known as NUꢀ1000 serve as competent supports for
the activation of methyltrioxorhenium (MTO) toward olefin meꢀ
tathesis. Itself inactive for olefin metathesis, MTO only becomes
an active catalyst when immobilized on the strongly acidic Lewis
acid sites of dehydrated NUꢀ1000. Uptake of MTO at the dehyꢀ
drated secondary building units (SBUs) occurs rapidly and quantiꢀ
tatively to produce a catalyst active in both gasꢀ and liquidꢀphase
processes. These results demonstrate for the first time the utility
of MOF SBUs for olefin metathesis, an academically and indusꢀ
trially relevant transformation.
30
31,32
ery
and efficient preparation
of methyltrioxorhenium
3
3–37
(MTO), a molecule with diverse catalytic competency.
The
for immobilized
38–40
most salient feature of this versatile model
rhenium oxide species in the context of heterogeneous OM catalyꢀ
sis is its inability to catalyze this transformation until activated on
an appropriate support. The surprisingly limited scope of supports
4
1–
capable of triggering OM activity from MTO include alumina
49
41,47,50–53
54,55
56
,
silicaꢀalumina,
niobia,
and zeolite HY.
INTRODUCTION
Owing to their wellꢀdefined, tunable structures, metalꢀorganic
frameworks (MOFs) are gaining traction as supports for heterogeꢀ
neous catalysis in largeꢀscale processes such as olefin valorizaꢀ
1–8
tion. Their wellꢀdefined active sites stand in contrast with the
structure of metals on traditional supports such as silica, alumina,
or zirconia, whose study is plagued by difficulties stemming from
their lack of periodicity, the diversity of potential binding sites,
9
–14
and differences based on preparative method.
One prominent
example of this challenge is that of heterogeneous olefin metatheꢀ
sis (OM) on immobilized molybdenum, tungsten, and rhenium
15–18
oxide catalysts (Figure S1).
Despite decades of research, unꢀ
Figure 1. Idealized molecular structures of the secondary
building units of a) NUꢀ1000 and b) dꢀNUꢀ1000; carboxylate
groups have been omitted for clarity.
certainties persist regarding the intimate mechanistic details and
the nature of the active species in these systems. Although MOFs
have been explored for OM catalysis, it has usually been in the
19,20
context of immobilizing wellꢀdefined homogeneous catalysts.
Yet, these materials are potentially excellent platforms for fundaꢀ
mental studies related to the largeꢀscale industrial (i.e. oxideꢀ
based) metathesis processes: their porosity leads to a high surface
area for catalyst immobilization and thus high catalyst loading,
while the conserved structure across SBUs narrows the number of
RESULTS AND DISCUSSION
In exploring OM activity with MTO, we were inspired by a reꢀ
cent report of MTO grafting on the zirconium SBUs (Figure 1a)
2
1–25
possibilities for active site speciation.
of
[Zr (µ ꢀO) (µ ꢀOH) (OH) (H O) ](TBAPy)
(NUꢀ1000;
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3
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2
4
2
The secondary building units (SBUs) are particularly relevant
targets for functionalization because they can be thought of as
nanoscale models of the metal oxides traditionally used as indusꢀ
57
TBAPy = 4,4′,4′′,4′′′ꢀ(pyreneꢀ1,3,6,8ꢀtetrayl)tetrakis(benzoate)).
In contrast to the high temperature atomic layer deposition graftꢀ
ing used therein, we found the autogenous vapor pressure of MTO
sufficient to allow its diffusion into the pores of NUꢀ1000 under
ambient conditions. Thus, placing ground MTO crystals (1 equivꢀ
2
6,27
trial catalyst supports.
Among supported OM catalysts, rheniꢀ
um oxideꢀbased systems stand out due to their activity at room
temperature and their broad tolerance to a range of heterofuncꢀ
alent per Zr SBU) in a vial with NUꢀ1000 leads to a slow but
6
tionalized6,28,2o9lefins when activated by main group alkyl
visible darkening of the MOF from yellow to dirty green over 48
h. Excess rhenium precursor can be removed from the resulting
MTO@NUꢀ1000 by heating to 100 °C under high vacuum (10
1
species.
These characteristics contrast with molybdenum
and tungsten systems, which are active only at significantly higher
–4
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Torr), conditions that are sufficient for MTO sublimation. Inducꢀ
Promisingly, uptake of 0.5 equivalents of MTO into dꢀNUꢀ
1000 was rapid and quantitative, giving a Re mass loading of
4.4±0.2 wt%, in good agreement with 4.2 wt% expected for the
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tively coupled plasma – atomic emission spectroscopy (ICPꢀAES)
analysis of digested MTO@NUꢀ1000 showed substoichiometric
rhenium incorporation (4.5±0.1 wt% as opposed to 7.8 wt% exꢀ
uptake of 0.5 Re per Zr cluster in MTO@dꢀNUꢀ1000. Moreover,
6
pected for a ratio of Re:Zr SBU = 1:1). Powder Xꢀray diffraction
heating MTO@dꢀNUꢀ1000 did not release any MTO, confirming
that all rhenium precursor is grafted onto the MOF support. As
before, crystallinity is retained and no rhenium oxide formation is
observed by PXRD analysis of MTO@dꢀNUꢀ1000 (Figure S6),
which otherwise shows homogeneous distribution of Re as judged
from the SEMꢀEDX mapping (Figure S8). Most notably, and
clearly indicative of its increased reactivity, brown MTO@dꢀNUꢀ
1000 is airꢀsensitive and discolors to yellow, the color of the parꢀ
ent dꢀNUꢀ1000 upon exposure to air (Figure S10). This contrasts
with the behavior of MTO@NUꢀ1000, which is not airꢀsensitive
and is inactive for OM, as discussed above.
6
(PXRD) analysis confirmed that MTO@NUꢀ1000 retains its crysꢀ
tallinity and that no crystalline rhenium oxide is formed under
these conditions (Figure S2). The material exhibits lower surface
area compared to the parent material, consistent with node funcꢀ
58
tionalization and a decreased pore volume (Figure S3). A uniꢀ
form rhenium distribution throughout the MOF particles was conꢀ
firmed by scanning electron microscopy ꢀ energy dispersive Xꢀray
spectroscopy (SEMꢀEDX) mapping (Figure S4).
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To probe the metathesis activity of MTO@NUꢀ1000, we moniꢀ
tored the formation of ethylene and 5ꢀdecene from the homomeꢀ
tathesis of 1ꢀhexene: no product formation was observed even
after 48 h of contact time at temperatures up to 60 °C (Figure S5).
The lack of reactivity highlighted a potential difference between
the Zr support in NUꢀ1000 and the traditional silica and/or alumiꢀ
na supports for MTO in OM. The Lewis acidity of the support has
been identified in this sense as one of the most critical factors in
Initial confirmation of OM activity with MTO@dꢀNUꢀ1000
1
came from the 1ꢀhexene test reaction: H NMR spectroscopy of a
reaction mixture in benzeneꢀd showed new resonances at 5.45
6
ppm and 5.25 ppm, indicating the formation of 5ꢀdecene and ethꢀ
ylene, respectively (Figure S12). Although the isomerization of
terminal olefins is an undesired sideꢀreaction on strongly acidic
39,43,49,52,54
activating MTO.
Indeed, as the weakest Lewis acid,
supports and can lead to costly and energyꢀintensive
51,53,56
silica does not engender metathesis activity despite its ability to
separations,
we did not observe any other internal olefins
53
bind MTO. Conversely, due to their more pronounced Lewis
other than 5ꢀdecene, the desired product (Figure S13). This sugꢀ
gests a moderate Lewis acidity and the absence of Brønsted acidic
sites in dꢀNUꢀ1000, which provides a middle ground between
successful MTO activation and deleterious olefin isomerization.
Control experiments showed that nonꢀgrafted dꢀNUꢀ1000 is not
competent for 1ꢀhexene metathesis reactivity even at 60 °C (Figꢀ
ure S11). Finally, PXRD analysis of the spent catalyst confirmed
retention of crystallinity during catalysis (Figure S18).
acidity, silicaꢀalumina and alumina both activate CH ReO for
3
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OM. The most commonly invoked interaction of Lewis acidic
centers involves coordination of MTO’s oxo group, which alters
the precursor’s electronic structure. Clearly, the presence of
strong Lewis acid sites is critical for the activation of MTO toꢀ
wards OM.
Conveniently, the Lewis acidity of the zirconiumꢀbased MOFs
can be augmented in a facile manner through highꢀtemperature
Encouraged by these results, we sought to address a more releꢀ
vant reaction in industrial OM catalysis: the onꢀpurpose formation
27,59,60
dehydration of the SBU.
In the case of NUꢀ1000, the loss of
8+
66,67
eight water molecules from [Zr (µ ꢀO) (µ ꢀOH) (OH) (H O) ]
leads to completely aprotic [Zr (µ ꢀO) ] nodes (Figure 1b).
These exhibit four Zr ions that are bound, on average, to two
fewer oxygen atoms and are thus more acidic than those in the
original SBU. We surmised that the dehydrated material (dꢀNUꢀ
of propylene by crossꢀmetathesis of ethylene with 2ꢀbutenes.
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+
61–63
The reverse reaction, propylene homometathesis to ethylene and
2ꢀbutene, is a good proxy for evaluating catalytic activity in this
transformation. It was thus used as an initial probe of gasꢀphase
catalytic activity with MTO@dꢀNUꢀ1000. At room temperature,
the catalyst mediates propylene metathesis with an initial TOF of
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4
+
1
000) would be a more active support for MTO both because of
–1
the increased Lewis acidity and because the absence of protons
near the presumed active site would prevent undesired protonation
86 hr after 10 min and a decaying rate profile typical of MTOꢀ
45
derived systems (Figures 2 and S15). Our system is less active
than reported MTO immobilized on alumina, which exhibits TOF
6
4,65
of Reꢀalkylidene species.
–1
of 2700 hr after 6 min under similar conditions. This difference
in reactivity also applies to MTO/SiO ꢀAl O , which has been
2
2
3
shown to be ten times more active than MTO/γꢀAl O in batch
2
3
49
experiments. However, it is important to note that this compariꢀ
son involves supports based on different Lewis acidic centers. To
the best of our knowledge no study on OM activity of MTO on
ZrO has been published. In addition to the previously mentioned
2
MTO deposited on silica, TiO [200] is also catalytically incompeꢀ
2
54
tent in the activation of MTO for OM.
The steadyꢀstate ratio of cisꢀ to transꢀ2ꢀbutene was approxiꢀ
mately 1.3 (Figure 2, inset); the slight preference for the less
thermodynamically stable product is in line with previous reports
of supported MTO catalysts and is due to the sterically crowded
45
profile of such species. No 1ꢀbutene formation was detected by
gas chromatography, paralleling the lack of isomerization obꢀ
served with liquid phase experiments (Figure S17). Importantly,
MTO@dꢀNUꢀ1000 remains active and displays 182 turnover
numbers after 20 hours (Figure S16). Mirroring the liquid phase
experiments, the spent MOF remains crystalline and porous, as
evidenced by PXRD and BET analysis (Figures S18 and S19). In
line with earlier experiments, NUꢀ1000 and MTO@NUꢀ1000
were essentially inactive for propylene metathesis under identical
conditions (Figures 2 and S14).
Figure 2. Propylene metathesis activity of MTO@dꢀNUꢀ1000
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on MTO interaction with heterogeneous supports suggests that
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more than one way of interaction might be operational.
CONCLUSION
In summary, although MTO binds to NUꢀ1000 both before and
after node dehydration, only the dehydrated MOF produces an
active olefin metathesis catalyst. This markedly different reactiviꢀ
ty is a testament to the significant difference in the Lewis acidity
4+
of the Zr ꢀbased SBUs before and after dehydration. This reactivꢀ
ity trend is in agreement with the observed increasing Lewis
acidity trend in transitioning from silica to silicaꢀalumina and
alumina. The results herein demonstrate for the first time that
MOF SBUs can enable catalytic olefin metathesis. In this context,
dꢀNUꢀ1000 joins a select group of heterogeneous supports capaꢀ
ble of activating MTO for this reaction. With OM activity thus
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established, future efforts in our lab will follow documented apꢀ
proaches for mechanistic investigations at MOF nodes
elucidate the precise nature of the Re active site in this system.
71–73
to
Figure 3. Partial DRIFTS spectrum of MTO@dꢀNUꢀ1000
ASSOCIATED CONTENT
Supporting Information
Experimental details, PXRD patterns, nitrogen isotherms, SEMꢀ
To gain information on the nature of Re species responsible for
catalysis, we grafted a higher loading of MTO into dꢀNUꢀ1000 to
increase the spectroscopic features observable by diffuse reflecꢀ
tance infrared Fourier transform spectroscopy (DRIFTS). Notaꢀ
bly, the Re uptake remains quantitative up to at least 23.2±0.7
wt%, which corresponds to approximately 3.6 Re equivalents per
SBU (for characterization see Figures S6, S7 and S9). DRIFTS
analysis of this more highly grafted MTO@dꢀNUꢀ1000 revealed
1
EDX maps, additional DRIFTS spectra, sample H NMR spectra
and GC traces, site time yield and TOF plots as well as the graphꢀ
ical representation of the plausible MTO binding mode are availaꢀ
ble in the supporting information pdf file.
AUTHOR INFORMATION
Corresponding Authors
–
1
bands at 995, 971, and 948 cm that are typically ascribed to the
symmetric and two asymmetric Re=O stretches, respectively
Eꢀmail: mdinca@mit.edu
Eꢀmail: yroman@mit.edu
68
(
Figure 3). Lifting of the asymmetric stretch degeneracy points
to a symmetry lower than the idealized C3v symmetry of MTO and
6
9
ORCID
is suggestive of rigidly immobilized species. Even though C–H
stretches from MTO are often diagnostic of the nature of the imꢀ
mobilized species, the parent MOF obscures the relevant 2800ꢀ
Maciej D. Korzyński: 0000ꢀ0002ꢀ6577ꢀ1821
Daniel F. Consoli: 0000ꢀ0002ꢀ1061ꢀ3391
Yuriy RománꢀLeshkov: 0000ꢀ0002ꢀ0025ꢀ4233
Mircea Dincă: 0000ꢀ0002ꢀ1262ꢀ1264
–1
3200 cm region in our system (Figure S20). However, MTO@dꢀ
–
1
NUꢀ1000 does display a sharp band at 3649 cm that is absent in
dꢀNUꢀ1000. It is known that pure MTO exhibits a weak combinaꢀ
–
1
Notes
tion band at 3637 cm originating from much more intense funꢀ
–
1
–1
70
The authors declare no competing financial interests. MDK and
DFC contributed equally.
damental modes at 740 cm and 2900 cm (Figure S21). Howꢀ
–1
ever, based on the intensity of the signal at 3649 cm observed in
MTO@dꢀNUꢀ1000, it is unlikely that this band originates from
MTO vibrational modes, given that the fundamentals giving rise
to this mode are not visible. Instead, based on comparisons with
the spectrum of activated NUꢀ1000, we tentatively ascribe the
ACKNOWLEDGMENT
This research was supported through a Research Agreement with
Saudi Aramco, a Founding Member of the MIT Energy Initiative.
The authors thank Prof. Chao Wang for his advice regarding the
preparation of alkyltin reagents, Dr. Robert Day for collection of
the SEMꢀEDX data and Mr. Wesley Transue for useful discusꢀ
sions.
–
1
sharp signal at 3649 cm to a bridging OꢀH group. To validate
this hypothesis, we prepared and deposited deuterated MTO (Figꢀ
ure S23) to investigate the expected isotopic shift associated with
the formation of OꢀD moieties. Indeed, the most pronounced
change in the DRIFTS spectrum of MTOꢀd3@dꢀNUꢀ1000 comꢀ
pared with the nonꢀdeuterated material is the disappearance of the
–1
band at 3649 cm– and the appearance of a qualitatively similar
REFERENCES
1
band at 2691 cm (Figure S24). The latter agrees well with the
(
1)
Cho, S.ꢀH.; Ma, B.; Nguyen, S. T.; Hupp, J. T.; Albrechtꢀ
Schmitt, T. E. A Metal–organic Framework Material That
Functions as an Enantioselective Catalyst for Olefin
Epoxidation. Chem. Commun. 2006, No. 24, 2563–2565.
Song, F.; Wang, C.; Falkowski, J. M.; Ma, L.; Lin, W.
Isoreticular Chiral MetalꢀOrganic Frameworks for Asymmetric
Alkene Epoxidation: Tuning Catalytic Activity by Controlling
Framework Catenation and Varying Open Channel Sizes. J. Am.
Chem. Soc. 2010, 132 (43), 15390–15398.
theoretical shift calculated using the harmonic oscillator approxiꢀ
–1
–1
mation (2657 cm ). An additional weak band at 2109 cm is in
the region expected for CꢀD stretches. Extensive studies on MTO
immobilized on alumina have shown that the active site is formed
by CꢀH bond scission to yield a bridging methylene species with
(2)
42
one of the oxygen atoms acting as an acceptor of a proton. We
expect that the node of dꢀNUꢀ1000 could also facilitate such proꢀ
ton migration (Figure S25), which would explain the reappearance
of the OꢀH stretch in the spectrum. However, the previous studies
(3)
Zhang, J.; Biradar, A. V.; Pramanik, S.; Emge, T. J.; Asefa, T.;
Li, J. A New Layered Metal–organic Framework as a Promising
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 6
Heterogeneous Catalyst for Olefin Epoxidation Reactions.
Chem. Commun. 2012, 48 (52), 6541–6543.
Mlinar, A. N.; Keitz, B. K.; Gygi, D.; Bloch, E. D.; Long, J. R.;
Bell, A. T. Selective Propene Oligomerization with Nickel(II)ꢀ
Based Metal–Organic Frameworks. ACS Catal. 2014, 4 (3),
(23)
(24)
(25)
Cohen, S. M.; Zhang, Z.; Boissonnault, J. A. Toward
“metalloMOFzymes”: Metal–Organic Frameworks with Singleꢀ
Site Metal Catalysts for SmallꢀMolecule Transformations.
Inorg. Chem. 2016, 55 (15), 7281–7290.
Xu, W.; Thapa, K. B.; Ju, Q.; Fang, Z.; Huang, W.
Heterogeneous Catalysts Based on Mesoporous Metal–organic
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(
4)
5)
7
17–721.
(
Metzger, E. D.; Brozek, C. K.; Comito, R. J.; Dincă, M.
Selective Dimerization of Ethylene to 1ꢀButene with a Porous
Catalyst. ACS Cent. Sci. 2016, 2 (3), 148–153.
Frameworks.
Coord.
Chem.
Rev.
2017,
doi:
10.1016/j.ccr.2017.10.014.
Rogge, S. M. J.; Bavykina, A.; Hajek, J.; Garcia, H.; Olivosꢀ
Suarez, A. I.; SepúlvedaꢀEscribano, A.; Vimont, A.; Clet, G.;
Bazin, P.; Kapteijn, F.; Daturi, M.; RamosꢀFernandez, E. V.;
Llabrés i Xamena, F. X.; Van Speybroeck, V.; Gascon, J.
Metal–organic and Covalent Organic Frameworks as SingleꢀSite
Catalysts. Chem. Soc. Rev. 2017, 46 (11), 3134–3184.
PlateroꢀPrats, A. E.; Mavrandonakis, A.; Gallington, L. C.; Liu,
Y.; Hupp, J. T.; Farha, O. K.; Cramer, C. J.; Chapman, K. W.
Structural Transitions of the MetalꢀOxide Nodes within Metal–
Organic Frameworks: On the Local Structures of NUꢀ1000 and
UiOꢀ66. J. Am. Chem. Soc. 2016, 138 (12), 4178–4185.
Rimoldi, M.; Howarth, A. J.; DeStefano, M. R.; Lin, L.;
Goswami, S.; Li, P.; Hupp, J. T.; Farha, O. K. Catalytic
Zirconium/HafniumꢀBased Metal–Organic Frameworks. ACS
Catal. 2017, 7 (2), 997–1014.
(6)
(7)
Comito, R. J.; Fritzsching, K. J.; Sundell, B. J.; SchmidtꢀRohr,
K.; Dincă, M. SingleꢀSite Heterogeneous Catalysts for Olefin
Polymerization Enabled by Cation Exchange in a MetalꢀOrganic
Framework. J. Am. Chem. Soc. 2016, 138 (32), 10232–10237.
Li, Z.; Peters, A. W.; Bernales, V.; Ortuño, M. A.; Schweitzer,
N. M.; DeStefano, M. R.; Gallington, L. C.; PlateroꢀPrats, A. E.;
Chapman, K. W.; Cramer, C. J.; Gagliardi, L.; Hupp, J. T.;
Farha, O. K. Metal–Organic Framework Supported Cobalt
Catalysts for the Oxidative Dehydrogenation of Propane at Low
Temperature. ACS Cent. Sci. 2017, 3 (1), 31–38.
Bernales, V.; Yang, D.; Yu, J.; Gümüꢁlü, G.; Cramer, C. J.;
Gates, B. C.; Gagliardi, L. Molecular Rhodium Complexes
Supported on the MetalꢀOxideꢀLike Nodes of Metal Organic
Frameworks and on Zeolite HY: Catalysts for Ethylene
Hydrogenation and Dimerization. ACS Appl. Mater. Interfaces
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(26)
(27)
(8)
(28)
(29)
Mol, J. C. Olefin Metathesis over Supported Rhenium Oxide
Catalysts. Catal. Today 1999, 51 (2), 289–299.
2
017, 9 (39), 33511–33520.
(
(
(
9)
Ma, Z.; Zaera, F. Heterogeneous Catalysis by Metals. In
Encyclopedia of Inorganic Chemistry; John Wiley & Sons, Ltd:
Chichester, UK, 2006; Vol. 30, pp 27–38.
Breysse, M.; Afanasiev, P.; Geantet, C.; Vrinat, M. Overview of
Support Effects in Hydrotreating Catalysts. Catal. Today 2003,
86 (1–4), 5–16.
Digne, M.; Sautet, P.; Raybaud, P.; Euzen, P.; Toulhoat, H. Use
of DFT to Achieve a Rational Understanding of AcidꢀBasic
Properties of γꢀAlumina Surfaces. J. Catal. 2004, 226 (1), 54–
68.
Joubert, J.; Delbecq, F.; Sautet, P.; Le Roux, E.; Taoufik, M.;
Thieuleux, C.; Blanc, F.; Copéret, C.; ThivolleꢀCazat, J.; Basset,
J. M. Molecular Understanding of Alumina Supported Singleꢀ
Site Catalysts by a Combination of Experiment and Theory. J.
Am. Chem. Soc. 2006, 128 (28), 9157–9169.
Gao, F.; Goodman, D. W. Model Catalysts: Simulating the
Complexities of Heterogeneous Catalysts. Annu. Rev. Phys.
Chem. 2012, 63 (1), 265–286.
Gates, B. C.; FlytzaniꢀStephanopoulos, M.; Dixon, D. A.; Katz,
A. Atomically Dispersed Supported Metal Catalysts:
Perspectives and Suggestions for Future Research. Catal. Sci.
Technol. 2017, 7 (19), 4259–4275.
Moses, A. W.; Leifeste, H. D.; Ramsahye, N. A.; Eckert, J.;
Scott, S. L. Supported Re Catalysts for Metathesis of
Functionalized Olefins. In Catalysis of Organic Reactions;
Schmidt, S. R., Ed.; CRC Press: Boca Raton, 2007; pp 13–22.
Beattie, I. R.; Jones, P. J. Methyltrioxorhenium. An AirꢀStable
Compound Containing a CarbonꢀRhenium Bond. Inorg. Chem.
1979, 18 (8), 2318–2319.
10)
11)
(30)
(31)
Herrmann, W. A.; Kuchler, J. G.; Felixberger, J. K.; Herdtweck,
E.; Wagner, W. Methylrhenium Oxides: Synthesis from R O
2 7
and Catalytic Activity in Olefin Metathesis. Angew. Chemie Int.
Ed. English 1988, 27 (3), 394–396.
Tosh, E.; Mitterpleininger, J. K. M.; Rost, A. M. J.; Veljanovski,
D.; Herrmann, W. A.; Kühn, F. E. Methyltrioxorhenium
Revisited: Improving the Synthesis for a Versatile Catalyst.
Green Chem. 2007, 9 (12), 1296.
Romão, C. C.; Kühn, F. E.; Herrmann, W. A. Rhenium(VII)
Oxo and Imido Complexes: Synthesis, Structures, and
Applications. Chem. Rev. 1997, 97 (8), 3197–3246.
Herrmann, W. A.; Kühn, F. E. Organorhenium Oxides †. Acc.
Chem. Res. 1997, 30 (4), 169–180.
Kühn, F. E.; Scherbaum, A.; Herrmann, W. A.
Methyltrioxorhenium and Its Applications in Olefin Oxidation,
Metathesis and Aldehyde Olefination. J. Organomet. Chem.
2004, 689 (24), 4149–4164.
(
12)
13)
(32)
(33)
(
(14)
(34)
(35)
(15)
Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis
Polymerization, 2 edition.; Academic Press, 1997.
(
16)
17)
Lwin, S.; Wachs, I. E. Olefin Metathesis by Supported Metal
Oxide Catalysts. ACS Catal. 2014, 4 (8), 2505–2520.
Gholampour, N.; Yusubov, M.; Verpoort, F. Investigation of the
Preparation and Catalytic Activity of Supported Mo, W, and Re
Oxides as Heterogeneous Catalysts in Olefin Metathesis. Catal.
Rev. 2016, 58 (1), 113–156.
Copéret, C.; ComasꢀVives, A.; Conley, M. P.; Estes, D. P.;
Fedorov, A.; Mougel, V.; Nagae, H.; NúñezꢀZarur, F.; Zhizhko,
P. A. Surface Organometallic and Coordination Chemistry
toward SingleꢀSite Heterogeneous Catalysts: Strategies,
Methods, Structures, and Activities. Chem. Rev. 2016, 116 (2),
323–421.
(36)
(37)
Jain, K. R.; Kühn, F. E. Immobilization of organorhenium(VII)
Oxides. J. Organomet. Chem. 2007, 692 (25), 5532–5540.
Hudson, A.; Betz, D.; Kühn, F. E.; JiménezꢀAlemán, G. H.;
Boland, W. Methyltrioxorhenium. In Encyclopedia of Reagents
for Organic Synthesis; John Wiley & Sons, Ltd: Chichester, UK,
2013; Vol. 1, pp 1–11.
Copéret, C. Design and Understanding of Heterogeneous Alkene
Metathesis Catalysts. Dalt. Trans. 2007, No. 47, 5498.
Lai, Y.ꢀY.; Bornand, M.; Chen, P. Homogeneous Model
Complexes for Supported Rhenia Metathesis Catalysts.
Organometallics 2012, 31 (21), 7558–7565.
(
(18)
(38)
(39)
(40)
(41)
Valla, M.; Conley, M. P.; Copéret, C. MeReO
3 2 3
/Al O and
(
19)
20)
Chołuj, A.; Zieliński, A.; Grela, K.; Chmielewski, M. J.
Metathesis@MOF: Simple and Robust Immobilization of Olefin
Metathesis Catalysts inside (Al)MILꢀ101ꢀNH . ACS Catal.
2
Me SnꢀActivated Re /Al Alkene Metathesis Catalysts
4
2
O
7
2 3
O
Have Similar Active Sites. Catal. Sci. Technol. 2015, 5 (3),
1438–1442.
2016, 6 (10), 6343–6349.
Rost, A. M. J.; Schneider, H.; Zoller, J. P.; Herrmann, W. A.;
Kühn, F. E. Methyltrioxorhenium Heterogenized on
Commercially Available Supporting Materials as Cyclooctene
Metathesis Catalyst. J. Organomet. Chem. 2005, 690 (21–22),
4712–4718.
Salameh, A.; Joubert, J.; Baudouin, A.; Lukens, W.; Delbecq,
3 3 2 3
F.; Sautet, P.; Basset, J. M.; Copéret, C. CH ReO on γꢀAl O :
Understanding Its Structure, Initiation, and Reactivity in Olefin
Metathesis. Angew. Chemie Int. Ed. 2007, 46 (21), 3870–3873.
Oikawa, T.; Masui, Y.; Tanaka, T.; Chujo, Y.; Onaka, M. Lewis
AcidꢀModified Mesoporous Alumina: A New Catalyst Carrier
(
Yuan, J.; Fracaroli, A. M.; Klemperer, W. G. Convergent
Synthesis of a Metal–Organic Framework Supported Olefin
Metathesis Catalyst. Organometallics 2016, 35 (12), 2149–
2
155.
(21)
Yoon, M.; Srirambalaji, R.; Kim, K. Homochiral Metal–Organic
Frameworks for Asymmetric Heterogeneous Catalysis. Chem.
Rev. 2012, 112 (2), 1196–1231.
Gascon, J.; Corma, A.; Kapteijn, F.; Llabrés i Xamena, F. X.
Metal Organic Framework Catalysis: Quo Vadisꢂ? ACS Catal.
(42)
(43)
(22)
2
014, 4 (2), 361–378.
ACS Paragon Plus Environment

Page 5 of 6
Journal of the American Chemical Society
for Methyltrioxorhenium in Metathesis of Olefins Bearing
Functional Groups. J. Organomet. Chem. 2007, 692 (1–3), 554–
61.
Salameh, A.; Baudouin, A.; Basset, J.ꢀM.; Copéret, C. Tuning
the Selectivity of AluminaꢀSupported (CH )ReO by Modifying
the Surface Properties of the Support. Angew. Chemie Int. Ed.
008, 47 (11), 2117–2120.
Salameh, A.; Baudouin, A.; Soulivong, D.; Boehm, V.; Roeper,
M.; Basset, J.ꢀM.; Copéret, C. CH ꢀReO on γꢀAl : Activity,
Selectivity, Active Site and Deactivation in Olefin Metathesis. J.
Catal. 2008, 253 (1), 180–190.
Wischert, R.; Copéret, C.; Delbecq, F.; Sautet, P. Revisiting the
Structure of Methyltrioxorhenium Chemisorbed on Alumina.
ChemCatChem 2010, 2 (7), 812–815.
Stekrova, M.; Zdenkova, R.; Vesely, M.; Vyskocilova, E.;
Cerveny, L. Immobilization of Methyltrioxorhenium on
Mesoporous Aluminosilicate Materials. Materials (Basel). 2014,
7 (12), 2650–2668.
Valla, M.; Wischert, R.; ComasꢀVives, A.; Conley, M. P.; Verel,
R.; Copéret, C.; Sautet, P. Role of Tricoordinate Al Sites in
Xiao, C.; Wang, S.; Farha, O. K. Efficient Capture of Perrhenate
and Pertechnetate by Mesoporous Zr Metal–Organic
Framework and Examination of Anion Binding Motifs. Chem.
Mater. 2018, 30 (4), 1277–1284.
Valenzano, L.; Civalleri, B.; Chavan, S.; Bordiga, S.; Nilsen, M.
H.; Jakobsen, S.; Lillerud, K. P.; Lamberti, C. Disclosing the
Complex Structure of UiOꢀ66 Metal Organic Framework: A
Synergic Combination of Experiment and Theory. Chem. Mater.
2011, 23 (7), 1700–1718.
Taddei, M. When Defects Turn into Virtues: The Curious Case
of ZirconiumꢀBased MetalꢀOrganic Frameworks. Coord. Chem.
Rev. 2017, 343, 1–24.
Planas, N.; Mondloch, J. E.; Tussupbayev, S.; Borycz, J.;
Gagliardi, L.; Hupp, J. T.; Farha, O. K.; Cramer, C. J. Defining
6
the Proton Topology of the Zr ꢀBased Metal–Organic
Framework NUꢀ1000. J. Phys. Chem. Lett. 2014, 5 (21), 3716–
3723.
Mondloch, J. E.; Katz, M. J.; Isley III, W. C.; Ghosh, P.; Liao,
P.; Bury, W.; Wagner, G. W.; Hall, M. G.; DeCoste, J. B.;
Peterson, G. W.; Snurr, R. Q.; Cramer, C. J.; Hupp, J. T.; Farha,
O. K. Destruction of Chemical Warfare Agents Using Metal–
organic Frameworks. Nat. Mater. 2015, 14 (5), 512–516.
Kim, I. S.; Borycz, J.; PlateroꢀPrats, A. E.; Tussupbayev, S.;
Wang, T. C.; Farha, O. K.; Hupp, J. T.; Gagliardi, L.; Chapman,
K. W.; Cramer, C. J.; Martinson, A. B. F. Targeted SingleꢀSite
MOF Node Modification: Trivalent Metal Loading via Atomic
Layer Deposition. Chem. Mater. 2015, 27 (13), 4772–4778.
LaPointe, A. M.; Schrock, R. R. Alkyl, Alkylidene, and
Alkylidyne Complexes of Rhenium. Organometallics 1995, 14,
1875–1884.
a
1
2
3
4
5
6
7
8
9
5
(
44)
45)
3
3
(59)
2
(
3
3
2 3
O
(60)
(61)
(
46)
47)
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1
1
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1
1
2
2
2
2
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5
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5
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0
1
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6
7
8
9
0
1
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4
5
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6
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3
4
5
6
7
8
9
0
(
(62)
(63)
(48)
3 3 2 3
CH ReO /Al O Olefin Metathesis Catalysts. J. Am. Chem. Soc.
2
016, 138 (21), 6774–6785.
(49)
Gallo, A.; Fong, A.; Szeto, K. C.; Rieb, J.; Delevoye, L.;
Gauvin, R. M.; Taoufik, M.; Peters, B.; Scott, S. L. Ligand
ExchangeꢀMediated Activation and Stabilization of a ReꢀBased
Olefin Metathesis Catalyst by Chlorinated Alumina. J. Am.
Chem. Soc. 2016, 138 (39), 12935–12947.
Herrmann, W. A.; Wagner, W.; Flessner, U. N.; Volkhardt, U.;
Komber, H. Methyltrioxorhenium as Catalyst for Olefin
Metathesis. Angew. Chemie Int. Ed. English 1991, 30 (12),
1636–1638.
Mathew, T. M.; du Plessis, J. A. K.; Prinsloo, J. J.
Methyltrioxorhenium on Silica–alumina as Metathesis Catalyst
of 1ꢀOctene. J. Mol. Catal. A Chem. 1999, 148 (1–2), 157–164.
Moses, A. W.; Ramsahye, N. A.; Raab, C.; Leifeste, H. D.;
Chattopadhyay, S.; Chmelka, B. F.; Eckert, J.; Scott, S. L.
Methyltrioxorhenium Interactions with Lewis Acid Sites of an
Amorphous Silica−Alumina. Organometallics 2006, 25 (9),
(
50)
51)
(64)
(65)
Chabanas, M.; Baudouin, A.; Copéret, C.; Basset, J.ꢀM.;
Lukens, W.; Lesage, A.; Hediger, S.; Emsley, L. Perhydrocarbyl
Re VII Complexes: Comparison of Molecular and Surface
Complexes. J. Am. Chem. Soc. 2003, 125 (2), 492–504.
(
(52)
(53)
(66)
Plotkin,
J.
S.
The
Propylene
Quandary
https://www.acs.org/content/acs/en/pressroom/cuttingꢀedgeꢀ
chemistry/theꢀpropyleneꢀquandary.html (accessed Jan 2, 2018).
Mol, J. C. Industrial Applications of Olefin Metathesis. J. Mol.
Catal. A Chem. 2004, 213 (1), 39–45.
Vaz, P. D.; RibeiroꢀClaro, P. J. A. The Role of CꢀH···O
Interactions in the Solid and LiquidꢀPhase Structures of
Methyltrioxo Rhenium. Eur. J. Inorg. Chem. 2005, 1836–1840.
Parker, S. F.; Herman, H. The Vibrational Spectrum of
(67)
(68)
2
157–2165.
Moses, A. W.; Raab, C.; Nelson, R. C.; Leifeste, H. D.;
Ramsahye, N. A.; Chattopadhyay, S.; Eckert, J.; Chmelka, B. F.;
Scott, S. L. Spectroscopically Distinct Sites Present in
Methyltrioxorhenium Grafted onto Silica−Alumina, and Their
Abilities to Initiate Olefin Metathesis. J. Am. Chem. Soc. 2007,
(69)
(70)
methyltrioxorhenium(VII). Spectrochim. Acta Part
Biomol. Spectrosc. 2000, 56 (6), 1123–1129.
A Mol.
1
29 (28), 8912–8920.
(
54)
55)
Buffon, R.; Auroux, A.; Lefebvre, F.; Leconte, M.; Choplin, A.;
Basset, J.ꢀM.; Herrmann, W. A. A Surface Organometallic
Approach to the Synthesis of RheniumꢀBased Catalysts for the
Mink, J.; Keresztury, G.; Stirling, A.; Herrmann, W. A.
Vibrational Spectroscopic and Force Field Studies of
organorhenium(VII) TrioxidesꢀI. Methyltrioxorhenium(VII),
ethyltrioxorhenium(VII) and (Nꢀpropyl)trioxorhenium(VII).
Spectrochim. Acta Part A Mol. Spectrosc. 1994, 50 (12), 2039–
2057.
Metzger, E. D.; Comito, R. J.; Hendon, C. H.; Dincă, M.
Mechanism of SingleꢀSite MoleculeꢀLike Catalytic Ethylene
Dimerization in NiꢀMFUꢀ4l. J. Am. Chem. Soc. 2017, 139 (2),
757–762.
Comito, R. J.; Metzger, E. D.; Wu, Z.; Zhang, G.; Hendon, C.
H.; Miller, J. T.; Dincă, M. Selective Dimerization of Propylene
with NiꢀMFUꢀ4l. Organometallics 2017, 36 (9), 1681–1683.
Dubey, R. J. C.; Comito, R. J.; Wu, Z.; Zhang, G.; Rieth, A. J.;
Hendon, C. H.; Miller, J. T.; Dincă, M. Highly Stereoselective
Heterogeneous Diene Polymerization by CoꢀMFUꢀ4lꢂ: A Singleꢀ
Site Catalyst Prepared by Cation Exchange. J. Am. Chem. Soc.
2017, 139 (36), 12664–12669.
3 3 2 5
Metathesis of Olefins: CH ReO /Nb O . J. Mol. Catal. 1992, 76
(1–3), 287–295.
(
Buffon, R.; Choplin, A.; Leconte, M.; Basset, J.ꢀM.; Touroude,
R.; Herrmann, W. A. Surface Organometallic Chemistry of
Rhenium: Attempts to Characterize a Surface Carbene in
Metathesis of Olefins with the Catalyst CH ReO /Nb O . J. Mol.
3 3 2 5
Catal. 1992, 72 (2), L7–L10.
Bein, T.; Huber, C.; Moller, K.; Wu, C.ꢀG.; Xu, L.
Methyltrioxorhenium Encapsulated in Zeolite Y: Tunable Olefin
Metathesis Catalyst. Chem. Mater. 1997, 9 (11), 2252–2254.
Rimoldi, M.; Hupp, J. T.; Farha, O. K. Atomic Layer Deposition
(71)
(
56)
57)
(72)
(73)
(
of Rhenium–Aluminum Oxide Thin Films and ReO
x
Incorporation in a Metal–Organic Framework. ACS Appl. Mater.
Interfaces 2017, 9 (40), 35067–35074.
Drout, R. J.; Otake, K.; Howarth, A. J.; Islamoglu, T.; Zhu, L.;
(58)
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