Reversible Metalation and Catalysis with a Scorpionate-like Metallo-ligand in a Metal-Organic Framework

Article abstract of DOI:10.1021/jacs.8b11085

The installation of metallo-ligands in metal-organic frameworks (MOFs) is an effective means to create site-isolated metal centers toward single-site heterogeneous catalysis. Although trispyrazolyborate (Tp) and tripyrazolylmethane (Tpm) form one of the most iconic classes of homogeneous catalysts, neither has been used as a metallo-ligand for the generation of MOFs thus far. Here, we show that upon in situ metalation with Cu^I, a tricarboxylated Tpm ligand reacts with ZrOCl₂ to generate a new MOF exhibiting neutral scorpionate-like chelating sites. These sites undergo for facile demetalation and remetalation with retention of crystallinity and porosity. When remetalated with Cu^I, the MOF exhibits spectroscopic features and catalytic activity for olefin cyclopropanation reactions that are similar to the molecular [Cu(CH₃CN)Tpm]PF₆ complex (Tpm? = tris(3,5-dimethylpyrazolyl)methane). These results demonstrate the inclusion of Tp or Tpm metallo-ligands in a MOF for the first time and provide a blueprint for immobilizing Tpm? catalysts in a spatially isolated and well-defined environment.

Full text of DOI:10.1021/jacs.8b11085

Subscriber access provided by University of Rhode Island | University Libraries
Communication
Reversible Metallation and Catalysis with a Scorpionate-
like Metallo-ligand in a Metal-Organic Framework
Chenyue Sun, Grigorii Skorupskii, Jin-hu Dou, Ashley M. Wright, and Mircea Dinca
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b11085 • Publication Date (Web): 30 Nov 2018
Downloaded from http://pubs.acs.org on November 30, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 6
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Reversible Metallation and Catalysis with a Scorpionate-like
Metallo-ligand in a Metal-Organic Framework
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Chenyue Sun, Grigorii Skorupskii, Jin-Hu Dou, Ashley M. Wright, Mircea Dincă*
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts
02139, United States
Supporting Information Placeholder
vents the formation of the homoleptic complexes, is piv-
ABSTRACT: The installation of metallo-ligands in metal-
otal for functional molecular chemistry with scorpi-
organic frameworks (MOFs) is an effective means to cre-
onates.11 Although bulky substituents are an effective en-
ate site-isolated metal centers towards single-site hetero-
try point for reactivity with scorpionate-bound metals, the
geneous catalysis. Although trispyrazolyborate (Tp) and
very need for bulky substituents would be obviated if the
tripyrazolylmethane (Tpm) form one of the most iconic
scorpionate ligand were immobilized in a solid matrix.
classes of homogeneous catalysts, neither has been used
Isolation of such complexes on silica,12,13 polysty-
as a metalloligand for the generation of MOFs thus far.
rene,14,15 and carbon materials16 illustrate this principle
Here, we show that upon in-situ metallation with CuI, a
well. However, the structural heterogeneity of these sup-
tricarboxylated Tpm ligand reacts with ZrOCl2 to gener-
ports makes any attempts to understand and control the
ate a new MOF exhibiting neutral scorpionate-like che-
lating sites. These sites allow for facile demetallation and
active site difficult.12–16
remetallation with retention of crystallinity and porosity.
When remetallated with CuI, the MOF exhibits similar
spectroscopic features and catalytic activity for olefin cy-
One class of hybrid solids that provide exceptional
structural uniformity are metal-organic frameworks
(MOFs).17 These materials’ ability to preserve a mole-
cule-like coordination environment in a rigid and well-
defined solid is highlighted by their utility as single-site
heterogeneous catalysts18,19 and as catalyst promoters.20
The anionic Tp itself is mimicked by the coordination en-
vironment of secondary building units (SBUs) of a series
of azolate-based MOFs.21,22 Metal substitution at these
SBUs23,24 provided heterogeneous catalysts for a range of
processes including ethylene oligomerization, polymeri-
zation, and C‒H amination.25–27 It is harder, however, to
devise or modify existing MOFs to mimic the neutral
Tpm ligand,28 whose metal complex chemistry often crit-
ically diverges from that of Tp.29–32
clopropanation
reactions
to
the
molecular
[Cu(CH3CN)Tpm*]PF6 complex (Tpm* = tris(3,5-di-
methylpyrazolyl)methane). These results demonstrate the
inclusion of Tp or Tpm metallo-ligands in a MOF for the
first time and provide a blueprint for immobilizing Tpm*
catalysts in a spatially-isolated and well-defined environ-
ment.
Seminal work by Trofimenko in the 1960s spurred the
synthesis and study of a massive number of scorpionate
metal complexes.1,2 The prototypical ligands, trispyrazol-
ylborate (Tp) and trispyrazolylmethane (Tpm), are
straightforward to synthesize and offer vast latitude of
electronic and steric control through functionalization of
the pyrazole rings.3 Scorpionate-type ligands often bind
metals in a facial, κ3 manner, thus leaving multiple sites
open for substrate binding. This has led to numerous ap-
plications in organometallic and bioinorganic chemis-
try.3–10 Despite their potential utility, the simplest, unfunc-
tionalized, and thus sterically most unencumbered scorpi-
onates are often ineffective for catalysis because they
preferentially form the homoleptic ML2 complexes with
first-row transition metals. Indeed, the installation of
bulky substituents at the pyrazole-3 position, which pre-
An alternative approach to site-isolation in MOFs is the
use of metallo-ligands, which can have the added benefit
of decoupling function, limited to the metallo-ligand,
from structure, supported by the SBU. A number of ca-
nonical chelating ligands and homogeneous catalysts
have been modified and introduced as linkers in MOFs.33–
44
Inspired by this methodology, we sought to isolate
MOFs with Tpm metallo-ligands. Here, we show that
1,1',1''-methanetriyltris(3,5-dimethyl-1H-pyrazole-4-car-
boxylic acid) (TpmC*), a Tpm-tricarboxylate, forms a
porous MOF with Zr SBUs, whose scorpionate moieties
can be post-synthetically demetallated and remetallated
readily, with retention of structural integrity. We further
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 6
demonstrate the utility of this new solid scorpionate cata-
(Figure S4), while the morphology and crystallinity re-
main unaltered, as confirmed by SEM and PXRD, respec-
tively (Figures S1, S5). Furthermore, 1H NMR of digested
2 shows no noticeable decomposition of the TpmC* lig-
and (Figure S4), allowing us to confidently describe 2 as
the free-base MOF, with a connectivity and topology
identical to 1 (Scheme 2).
lyst with the use of CuI-metallated MOF in cyclopropa-
nation catalysis.
1
2
3
4
5
6
7
Scheme 1. Synthesis of 1
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Direct reaction of TpmC* with ZrOCl2 led to exclusive
formation of amorphous materials, likely due to the flex-
ibility of the ligand, whose idealized C3v symmetry is not
favored in the absence of a metal ion. To lock the ligand
into the C3v symmetry, we reasoned that metallation may
be necessary prior to or concomitant with MOF for-
mation. Indeed, reaction of TpmC* with ZrOCl2 in the
presence of excess CuI and benzoic acid in N,N-dimethyl-
formamide (DMF) at 120 °C for 48 hours yields
{[Zr6O4(OH)4(C6H5COO)4]3(CuITpmC*)8} (1) as
a
white microcrystalline powder (Scheme 1). Because cu-
bic microcrystals of 1 (Figure 1c, S1) are too small for
single-crystal X-ray diffraction analysis, the structure of
1 was determined by Rietveld analysis of high-quality
powder X-ray diffraction (PXRD) data (Figure S2). The
ꢂ
MOF crystallizes in the cubic ꢀꢁ3ꢁ space group with
three-dimensionally interconnected channels lined by io-
dide anions pointing towards the center of the pores (Fig-
ure 1a). The idealized45 accessible pore diameter is 8.3 Å.
Because each Zr6O4(OH)4(CO2)12 SBU is 8-connected,
and each metallo-ligand bridges three SBUs, the MOF is
a 3,8-connected network with the the topology, similar to
BUT-12,46 another zirconium-based MOF with three-fold
symmetric ligands, and first observed in a tetrazolate
MOF.47 This topology also gives rise to vertex-sharing
octahedral cages with accessible cavities of 8.1 Å diame-
ter and windows of 2.5 Å, in which the SBUs constitute
vertices and linkers act as triangular faces. Benzoates,
H2O, or HO– complete the four vacancies in the equatorial
σh plane of each SBU. Within the metallo-ligand, CuI
adopts a distorted pseudotetrahedral geometry (Figure 1b)
with bond distances and angles nearly identical to those
found in molecular Tpm*CuI.48
Figure 1. (a) Partial X-ray diffraction structure of 1. Guest
molecules and benzoates are omitted for clarity. (b) Close-
up view of the Tpm*-like coordination environment. (c)
Scanning electron microscopy (SEM) image of 1.
Thermogravimetric analyses (TGA) showed that
whereas 1 has no significant mass loss up to 250 °C, 2
exhibits rapid weight loss above 180 °C (Figure S6). Even
heating 2 at 120 °C under dynamic vacuum for approxi-
mately 15 hours already leads to loss of crystallinity, as
may be expected for a MOF made with the more flexible
free-base ligand. Therefore, 2 was activated under dy-
namic vacuum at only 110 °C. An N2 adsorption for acti-
vated 2 at 77 K revealed a permanently porous material
displaying a Type I isotherm whose BET fit gave an ap-
parent surface area of 1795 ± 15 m2/g (Figure S7).
The ligands in 1 are quantitatively demetallated and
made available for ulterior metal sequestration by a sim-
ple acid treatment. Thus, reacting as-synthesized 1 with a
mixture of DMF and HCl reduces the Cu content of the
MOF from 7.54 Cu per formula unit to essentially zero,
as determined by inductively-coupled plasma-mass spec-
trometry (ICP-MS). This treatment thus provides the Cu-
free MOF {[Zr6O4(OH)4X4(H2O)4]3(TpmC*)8} (2, X =
HCOO– or HO–). X-ray photoelectron spectroscopy (XPS)
further confirmed the absence of Cu in 2 (Figure S3). Im-
portantly, acid treatment also removes all bound benzo-
ates, as determined by 1H NMR of a digested sample of 2
2
ACS Paragon Plus Environment

Page 3 of 6
Journal of the American Chemical Society
Table 1. Olefin cyclopropanation reactivity with 3a
Scheme 2. Post-synthetic demetallation and remetalla-
tion of 1
1
2
3
4
5
6
7
8
9
entry substrate
yield (%)b
95c
83c
1
styrene
2d
styrene
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
With free-base 2 in hand, we sought to demonstrate the
3
1-octene
81c
64e
84c
32c
utility of this material towards catalysis by remetallating
the TpmC* ligands. As proof of principle, we chose to
emulate the reactivity of the molecular complex
[(CH3CN)CuITpm*]PF6, a known homogeneous olefin
cyclopropanation catalyst49 easily prepared by reaction of
Tpm* with [Cu(CH3CN)4]PF6.50 Similar to the molecular
synthesis, soaking activated 2 in an acetonitrile solution
of [Cu(CH3CN)4]BF4 gives rise to crystalline
{[Zr6O4(OH)4(X)4(H2O)4]3[Cu(CH3CN)BF4]x(TpmC*)8}
(3, x ≈ 0 – 4, X = HO– or HCOO–) (Scheme 2, Figure S5).
Surprisingly, the final metallation level plateaus at ap-
proximately 4 Cu equivalents per formula unit, or 50% of
the available TpmC* ligands (Figure S8). Although metal
ions can attach to Zr clusters,51–54 a control experiment
where NU-1000, a material with similar 8-connected
SBUs but no metal-chelating ligands,55 was treated with
the same CuI precursor showed minimal incorporation of
CuI (SI). Thus, in 3, the majority of copper ions are ligated
within the TpmC* scorpionate pocket. Upon activation at
95 °C, 3 exhibits a BET surface area of 1554 ± 5 m2/g,
slightly lower than that of 2, as expected with the intro-
4
cyclohexene
2,5-dimethyl-2,4-hexadiene
methyl 2-furoate
5
6
a40 µM EDAA in 6 ml CH2Cl2 was added into a mixture
of 4 mg 3, 2 ml CH2Cl2 and 2.4 mmol substrate over 5 hours.
The mixture was stirred for another 9 hours before analysis
by 1H NMR and GC. bCombined yield of trans and cis (endo
and exo) diastereomers, calculated based on amount of
EDAA. cDetermined by 1H NMR. dThe reaction was stopped
1 hour after the addition of EDAA. eDetermined by GC-FID.
Furthermore, using Cu(I)-metallated NU-1000 as catalyst,
where the only possible CuI species are those attached to
the Zr SBUs, produced a yield of only 12% after 14 hours
(SI), compared to 95% for 3 under identical conditions.
The heterogeneous nature of 3 was confirmed by a hot
filtration experiment (Figure S10), which indicated that
no catalytically competent Cu species are leached into the
supernatant. In addition, the solid recovered after reaction
retained its crystallinity (Figure S5), confirming the struc-
tural integrity of 3 under catalytic conditions. Compared
with other copper-based solid catalysts for cyclopropana-
tion,57–60 3 uniquely combines the merit of high produc-
tivity with uniform, well-defined active sites. Importantly,
and portending to other potential applications in catalysis,
3 efficiently promotes carbene insertion into C‒H bonds
in cyclohexane, producing ethyl cyclohexylacetate in 67%
yield, surpassing the activity of the analogous homogene-
ous catalyst, which produces a yield of only 30% under
comparable conditions.49
‒
duction of [Cu(CH3CN)]+ moieties and BF4 within the
pores (Figure S7). Additional evidence for the scorpi-
onate coordination environment of Cu within 3 comes
from diffuse reflectance infrared Fourier transform spec-
troscopy (DRIFTS) analysis upon dosing with carbon
monoxide. The strong band at 2110 cm‒1 (Figure S9) is
very close to the reported value of 2113 cm‒1 for the anal-
ogous molecular complex [Cu(CO)Tpm*]PF6.50 Finally,
the major components of the Cu2p peaks in the XPS spec-
trum of 3 are similar to those found in the XPS spectrum
of 1, with additional minor components ascribed to either
small Cu deposits on the Zr clusters or inadvertent partial
oxidation of 3 during sample manipulation for XPS anal-
ysis (Figure S3).
In line with the activity of molecular [CuTpm]+ com-
plexes,49,56 3 is an efficient heterogeneous catalyst for ole-
fin cyclopropanation. Slow addition of a CH2Cl2 solution
of ethyl diazoacetate (EDAA) to a suspension of 3 and an
olefin substrate in CH2Cl2 under inert atmosphere pro-
duces cyclopropanes in yields comparable to molecular
catalysts (Table 1). A control reaction using 2, the
demetallated version of 3, as catalyst showed no detecta-
ble catalytic activity (less than 0.1% yield by 1H NMR).
In summary,
a
tricarboxyl-trispyrazolylmethane
metallo-ligand produces a MOF where neutral scorpi-
onate-like moieties can be demetallated and remetallated
readily, with preservation of crystallinity and porosity.
The utility of this first example of a Tpm-like environ-
ment in a MOF was demonstrated through cyclopropana-
tion catalysis enabled by CuI species installed post-syn-
thetically into the MOF. Ongoing studies suggest that the
same strategy is effective for installing other first row
transition metals into this MOF, which will prove espe-
cially useful for metal ions that prefer to form homoleptic
bis-Tpm complexes under homogeneous conditions. This
work therefore represents a blueprint for heterogenizing
other Tpm-based homogeneous catalysts that could ben-
efit from site-isolation, and may find further applications
3
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 6
Dinitrogen Complexes of First Row Transition Metals (Cr–Co).
in gas separations, where open metal sites are often re-
quired for selective adsorption.
Eur. J. Inorg. Chem. 2016, 2016 (15–16), 2349–2356.
Calabrese, J. C.; Trofimenko, S.; Thompson, J. S. A New Class
of Polypyrazolylborate Ligands. J. Chem. Soc. Chem. Commun.
1986, 530 (14), 1122–1123.
Diaz-Requejo, M. M.; Belderrain, T. R.; Nicasio, M. C.; Perez, P.
J. From Homogeneous to Heterogeneous Catalysis: Novel
Anchoring of Polypyrazolylborate Copper(I) Complexes on
Silica Gel through Classical and Nonclassical Hydrogen Bonds.
Use as Catalysts of the Olefin Cyclopropanation Reaction.
Organometallics 2000, 19 (3), 285–289.
1
2
3
4
5
6
7
8
(11)
(12)
ASSOCIATED CONTENT
Supporting Information.
Experimental details, Figure S1-S11, Table S1-S2 (PDF)
Crystallographic data for 1 (CIF)
AUTHOR INFORMATION
(13)
(14)
(15)
(16)
Machado, K.; Mukhopadhyay, S.; Mishra, G. S. Nanoparticles
Silica Anchored Cu(II) and V(IV) Scorpionate Complexes for
Selective Catalysis of Cyclohexane Oxidation. J. Mol. Catal. A
Chem. 2015, 400, 139–146.
9
Corresponding Author
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
*mdinca@mit.edu
Desrochers, P. J.; Corken, A. L.; Tarkka, R. M.; Besel, B. M.;
Mangum, E. E.; Linz, T. N. A Simple Route to Single-
Scorpionate Nickel(II) Complexes with Minimum Steric
Requirements. Inorg. Chem. 2009, 48 (8), 3535–3541.
Desrochers, P. J.; Besel, B. M.; Corken, A. L.; Evanov, J. R.;
Hamilton, A. L.; Nutt, D. L.; Tarkka, R. M. Immobilized Boron-
Centered Heteroscorpionates: Heterocycle Metathesis and
Coordination Chemistry. Inorg. Chem. 2011, 50 (5), 1931–1941.
de Almeida, M. P.; Martins, L. M. D. R. S.; Carabineiro, S. A. C.;
Lauterbach, T.; Rominger, F.; Hashmi, A. S. K.; Pombeiro, A. J.
L.; Figueiredo, J. L. Homogeneous and Heterogenised New Gold
C-Scorpionate Complexes as Catalysts for Cyclohexane
Oxidation. Catal. Sci. Technol. 2013, 3 (11), 3056.
Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The
Chemistry and Applications of Metal-Organic Frameworks.
Science. 2013, 341 (6149), 1230444.
Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.;
Hupp, J. T. Metal–Organic Framework Materials as Catalysts.
Chem. Soc. Rev. 2009, 38 (5), 1450.
Rogge, S. M. J.; Bavykina, A.; Hajek, J.; Garcia, H.; Olivos-
Suarez, A. I.; Sepúlveda-Escribano, A.; Vimont, A.; Clet, G.;
Bazin, P.; Kapteijn, F.; Daturi, M.; Ramos-Fernandez, E. V.;
Llabrés i Xamena, F. X.; Van Speybroeck, V.; Gascon, J. Metal–
Organic and Covalent Organic Frameworks as Single-Site
Catalysts. Chem. Soc. Rev. 2017, 46 (11), 3134–3184.
Zhao, M.; Yuan, K.; Wang, Y.; Li, G.; Guo, J.; Gu, L.; Hu, W.;
Zhao, H.; Tang, Z. Metal–Organic Frameworks as Selectivity
Regulators for Hydrogenation Reactions. Nature 2016, 539
(7627), 76–80.
Denysenko, D.; Grzywa, M.; Tonigold, M.; Streppel, B.; Krkljus,
I.; Hirscher, M.; Mugnaioli, E.; Kolb, U.; Hanss, J.; Volkmer, D.
Elucidating Gating Effects for Hydrogen Sorption in MFU-4-
Type Triazolate-Based Metal-Organic Frameworks Featuring
Different Pore Sizes. Chem. - A Eur. J. 2011, 17 (6), 1837–1848.
Wang, L.; Morales, J.; Wu, T.; Zhao, X.; Beyermann, W. P.; Bu,
X.; Feng, P. Assembly of Super-Supertetrahedral Metal-Organic
Clusters into a Hierarchical Porous Cubic Framework. Chem.
Commun. 2012, 48 (60), 7498–7500.
Denysenko, D.; Werner, T.; Grzywa, M.; Puls, A.; Hagen, V.;
Eickerling, G.; Jelic, J.; Reuter, K.; Volkmer, D. Reversible Gas-
Phase Redox Processes Catalyzed by Co-Exchanged MFU-
4l(Arge). Chem. Commun. 2012, 48 (9), 1236–1238.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This research was supported through a Research Agreement
with Saudi Aramco, a Founding Member of the MIT Energy
Initiative. The high-resolution PXRD was collected at beam-
line 11-BM of Advanced Photon Source, Argonne National
Laboratory, which is supported by the U.S. Department of
Energy, Office of Science, Office of Basic Energy Sciences,
under Contract No. DE-AC02-06CH11357. We thank R.
McGillicuddy and Prof. J. Mason for assistance with TGA
measurements. We also thank Y. Zhou, H. Zhang, and Prof.
S.Buchwald for assistance with GC measurements. M. Kor-
zyński is acknowledged for providing NU-1000. We thank
Dr. C. Brown for discussions on the Rietveld refinement.
(17)
(18)
(19)
REFERENCES
(20)
(21)
(1)
Trofimenko, S. Geminal Poly(1-Pyrazolyl)Alkanes and Their
Coordination Chemistry. J. Am. Chem. Soc. 1970, 92 (17), 5118–
5126.
(2)
Trofimenko, S. Boron-Pyrazole Chemistry. IV. Carbon- and
Boron-Substituted Poly[(1-Pyrazolyl) Borates]. J. Am. Chem.
Soc. 1967, 89 (24), 6288–6294.
(3)
(4)
Trofimenko, S. Recent Advances in Poly(Pyrazolyl)Borate
(Scorpionate) Chemistry. Chem. Rev. 1993, 93 (3), 943–980.
Kitajima, N.; Tolman, W. B. Coordination Chemistry with
Sterically Hindered Hydrotris(Pyrazoly1)Borate Ligands:
Organometallic and Bioinorganic Perspectives. Prog. Inorg.
Chem. 1995, 43, 419–531.
(22)
(23)
(5)
(6)
Bigmore, H. R.; Lawrence, S. C.; Mountford, P.; Tredget, C. S.
Coordination, Organometallic and Related Chemistry of
Tris(Pyrazolyl)Methane Ligands. Dalton Trans. 2005, No. 4,
635.
McKeown, B. A.; Lee, J. P.; Mei, J.; Cundari, T. R.; Gunnoe, T.
B. Transition Metal Mediated C–H Activation and
Functionalization: The Role of Poly(Pyrazolyl)Borate and
Poly(Pyrazolyl)Alkane Ligands. Eur. J. Inorg. Chem. 2016, 2016
(15–16), 2296–2311.
(24)
(25)
(26)
Brozek, C. K.; Bellarosa, L.; Soejima, T.; Clark, T. V.; Lõpez, N.;
Dincǎ, M. Solvent-Dependent Cation Exchange in Metal-Organic
Frameworks. Chem. - A Eur. J. 2014, 20 (23), 6871–6874.
Metzger, E. D.; Brozek, C. K.; Comito, R. J.; Dinca, M. Selective
Dimerization of Ethylene to 1-Butene with a Porous Catalyst.
ACS Cent. Sci. 2016, 2 (3), 148–153.
Comito, R. J.; Fritzsching, K. J.; Sundell, B. J.; Schmidt-Rohr,
K.; Dincă, M. Single-Site Heterogeneous Catalysts for Olefin
Polymerization Enabled by Cation Exchange in a Metal-Organic
Framework. J. Am. Chem. Soc. 2016, 138 (32), 10232–10237.
Wang, L.; Agnew, D. W.; Yu, X.; Figueroa, J. S.; Cohen, S. M.
A Metal–Organic Framework with Exceptional Activity for C−H
Bond Amination. Angew. Chemie - Int. Ed. 2018, 57 (2), 511–
515.
(7)
(8)
Martins, L. M. D. R. S.; Pombeiro, A. J. L. Water-Soluble C-
Scorpionate Complexes – Catalytic and Biological Applications.
Eur. J. Inorg. Chem. 2016, 2016 (15–16), 2236–2252.
Martins, L. M. D. R. S.; Pombeiro, A. J. L. Tris(Pyrazol-1-
Yl)Methane Metal Complexes for Catalytic Mild Oxidative
Functionalizations of Alkanes, Alkenes and Ketones. Coord.
Chem. Rev. 2014, 265 (1), 74–88.
(27)
(9)
Mukherjee, A.; Cranswick, M. A.; Chakrabarti, M.; Paine, T. K.;
Fujisawa, K.; Münck, E.; Que, L. Oxygen Activation at
Mononuclear Nonheme Iron Centers: A Superoxo Perspective.
Inorg. Chem. 2010, 49 (8), 3618–3628.
(28)
(29)
Kivi, C. E. W. Metal-Organic Frameworks of Pyrazolate
Derivatives: Synthesis and Applications for Chemical Sensing,
Gas Separation, and Catalysis, University of Toronto, 2017.
Burgess, S. A.; Joslin, E. E.; Gunnoe, T. B.; Cundari, T. R.; Sabat,
(10)
Cummins, D. C.; Yap, G. P. A.; Theopold, K. H. Scorpionates of
the “Tetrahedral Enforcer” Variety as Ancillary Ligands for
4
ACS Paragon Plus Environment

Page 5 of 6
Journal of the American Chemical Society
M.; Myers, W. H. Hydrophenylation of Ethylene Using a Cationic
Ru( II ) Catalyst: Comparison to a Neutral Ru( II ) Catalyst.
Chem. Sci. 2014, 5 (11), 4355–4366.
(47)
(48)
(49)
(50)
(51)
Dincǎ, M.; Dailly, A.; Liu, Y.; Brown, C. M.; Neumann, D. A.;
Long, J. R. Hydrogen Storage in a Microporous Metal−Organic
Framework with Exposed Mn2+ Coordination Sites. J. Am. Chem.
Soc. 2006, 128 (51), 16876–16883.
Haldón, E.; Álvarez, E.; Nicasio, M. C.; Pérez, P. J. Copper(I)
Complexes with Trispyrazolylmethane Ligands: Synthesis,
Characterization, and Catalytic Activity in Cross-Coupling
Reactions. Inorg. Chem. 2012, 51 (15), 8298–8306.
Rodríguez, P.; Caballero, A.; Díaz-Requejo, M. M.; Nicasio, M.
C.; Pérez, P. J. Very Efficient, Reusable Copper Catalyst for
Carbene Transfer Reactions under Biphasic Conditions Using
Ionic Liquids. Org. Lett. 2006, 8 (4), 557–560.
1
2
3
4
5
(30)
(31)
Fujisawa, K.; Ono, T.; Ishikawa, Y.; Amir, N.; Miyashita, Y.;
Okamoto, K. I.; Lehnert, N. Structural and Electronic Differences
of Copper(I) Complexes with Tris(Pyrazolyl)Methane and
Hydrotris(Pyrazolyl)Borate Ligands. Inorg. Chem. 2006, 45 (4),
1698–1713.
Cvetkovic, M.; Batten, S. R.; Moubaraki, B.; Murray, K. S.;
Spiccia, L. Copper(I) Tris(Pyrazolyl)Methane Complexes and
Their Reactivity towards Dioxygen. Inorganica Chim. Acta 2001,
324 (1–2), 131–140.
Seymore, S. B.; Brown, S. N. Charge Effects on Oxygen Atom
Transfer. Inorg. Chem. 2000, 39 (2), 325–332.
Kitaura, R.; Onoyama, G.; Sakamoto, H.; Matsuda, R.; Noro, S.
I.; Kitagawa, S. Immobilization of a Metallo Schiff Base into a
Microporous Coordination Polymer. Angew. Chemie - Int. Ed.
2004, 43 (20), 2684–2687.
Bloch, E. D.; Britt, D.; Lee, C.; Doonan, C. J.; Uribe-romo, F. J.;
Furukawa, H.; Long, J. R.; Yaghi, O. M. Metal Insertion in a
Microporous Metal - Organic Framework Lined with 2 , 2 ′ -
Bipyridine. J. Am. Chem. Soc. 2010, 132, 14382–14384.
Burgess, S. A.; Kassie, A.; Baranowski, S. A.; Fritzsching, K. J.;
Schmidt-Rohr, K.; Brown, C. M.; Wade, C. R. Improved
Catalytic Activity and Stability of a Palladium Pincer Complex
by Incorporation into a Metal-Organic Framework. J. Am. Chem.
Soc. 2016, 138 (6), 1780–1783.
Fang, X.; Shang, Q.; Wang, Y.; Jiao, L.; Yao, T.; Li, Y.; Zhang,
Q.; Luo, Y.; Jiang, H.-L. Single Pt Atoms Confined into a Metal-
Organic Framework for Efficient Photocatalysis. Adv. Mater.
2018, 30 (7), 1705112.
6
7
8
9
(32)
(33)
Reger, D. L.; Collins, J. E.; Rheingold, A. L.; Liable-Sands, L.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
M.
Synthesis
and
Characterization
of
Cationic
[Tris(Pyrazolyl)Methane]Copper(I) Carbonyl and Acetonitrile
Complexes. Organometallics 1996, 15 (8), 2029–2032.
Ji, P.; Manna, K.; Lin, Z.; Urban, A.; Greene, F. X.; Lan, G.; Lin,
W. Single-Site Cobalt Catalysts at New Zr 8 (µ 2 -O) 8 (µ 2 -OH) 4
Metal-Organic Framework Nodes for Highly Active
Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles.
J. Am. Chem. Soc. 2016, 138 (37), 12234–12242.
Ikuno, T.; Zheng, J.; Vjunov, A.; Sanchez-Sanchez, M.; Ortuño,
M. A.; Pahls, D. R.; Fulton, J. L.; Camaioni, D. M.; Li, Z.; Ray,
D.; Mehdi, B. L.; Browning, N. D.; Farha, O. K.; Hupp, J. T.;
Cramer, C. J.; Gagliardi, L.; Lercher, J. A. Methane Oxidation to
Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000
Metal–Organic Framework. J. Am. Chem. Soc. 2017, 139 (30),
10294–10301.
Korzyński, M. D.; Consoli, D. F.; Zhang, S.; Román-Leshkov,
Y.; Dincă, M. Activation of Methyltrioxorhenium for Olefin
Metathesis in a Zirconium-Based Metal–Organic Framework. J.
Am. Chem. Soc. 2018, 140 (22), 6956–6960.
Liu, J.; Ye, J.; Li, Z.; Otake, K.; Liao, Y.; Peters, A. W.; Noh, H.;
Truhlar, D. G.; Gagliardi, L.; Cramer, C. J.; Farha, O. K.; Hupp,
J. T. Beyond the Active Site: Tuning the Activity and Selectivity
(34)
(35)
(52)
(36)
(37)
(38)
(39)
(40)
(41)
(42)
(43)
(44)
(53)
(54)
Wang, C.; Xie, Z.; deKrafft, K. E.; Lin, W. Doping Metal–
Organic Frameworks for Water Oxidation, Carbon Dioxide
Reduction, and Organic Photocatalysis. J. Am. Chem. Soc. 2011,
133 (34), 13445–13454.
Shultz, A. M.; Sarjeant, A. A.; Farha, O. K.; Hupp, J. T.; Nguyen,
S. T. Post-Synthesis Modification of a Metal-Organic Framework
to Form Metallosalen-Containing MOF Materials. J. Am. Chem.
Soc. 2011, 133 (34), 13252–13255.
Feng, D.; Gu, Z.-Y.; Li, J.-R.; Jiang, H.-L.; Wei, Z.; Zhou, H.-C.
Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-
Organic Frameworks with Ultrahigh Stability as Biomimetic
Catalysts. Angew. Chemie Int. Ed. 2012, 51 (41), 10307–10310.
Anderson, J. S.; Gallagher, A. T.; Mason, J. A.; Harris, T. D. A
Five-Coordinate Heme Dioxygen Adduct Isolated within a
Metal–Organic Framework. J. Am. Chem. Soc. 2014, 136 (47),
16489–16492.
Falkowski, J. M.; Sawano, T.; Zhang, T.; Tsun, G.; Chen, Y.;
Lockard, J. V.; Lin, W. Privileged Phosphine-Based Metal-
Organic Frameworks for Broad-Scope Asymmetric Catalysis. J.
Am. Chem. Soc. 2014, 136 (14), 5213–5216.
Bloch, W. M.; Burgun, A.; Coghlan, C. J.; Lee, R.; Coote, M. L.;
Doonan, C. J.; Sumby, C. J. Capturing Snapshots of Post-
Synthetic Metallation Chemistry in Metal-Organic Frameworks.
Nat. Chem. 2014, 6 (10), 906–912.
Cohen, S. M.; Zhang, Z.; Boissonnault, J. A. Toward
“MetalloMOFzymes”: Metal-Organic Frameworks with Single-
Site Metal Catalysts for Small-Molecule Transformations. Inorg.
Chem. 2016, 55 (15), 7281–7290.
He, J.; Waggoner, N. W.; Dunning, S. G.; Steiner, A.; Lynch, V.
M.; Humphrey, S. M. A PCP Pincer Ligand for Coordination
Polymers with Versatile Chemical Reactivity: Selective
Activation of CO2 Gas over CO Gas in the Solid State. Angew.
Chemie - Int. Ed. 2016, 55 (40), 12351–12355.
of a Metal–Organic Framework-Supported Ni Catalyst for
Ethylene Dimerization. J. Am. Chem. Soc. 2018, 140 (36),
11174–11178.
(55)
(56)
Mondloch, J. E.; Bury, W.; Fairen-Jimenez, D.; Kwon, S.;
Demarco, E. J.; Weston, M. H.; Sarjeant, A. A.; Nguyen, S. T.;
Stair, P. C.; Snurr, R. Q.; Farha, O. K.; Hupp, J. T. Vapor-Phase
Metalation by Atomic Layer Deposition in a Metal-Organic
Framework. J. Am. Chem. Soc. 2013, 135 (28), 10294–10297.
Díaz-Requejo, M. M.; Caballero, A.; Belderraín, T. R.; Nicasio,
M. C.; Trofimenko, S.; Pérez, P. J. Copper(I)-Homoscorpionate
Catalysts for the Preferential, Kinetically Controlled Cis
Cyclopropanation of α-Olefins with Ethyl Diazoacetate. J. Am.
Chem. Soc. 2002, 124 (6), 978–983.
Fraile, J. M.; García, J. I.; Mayoral, J. A. Cyclopropanation
Reactions Catalysed by Copper(II)-Exchanged Clays and
Zeolites. Influence of the Catalyst on the Selectivity. Chem.
Commun. 1996, 1 (11), 1319–1320.
Dıaz-Requejo, M. M.; Nicasio, M. C.; Perez, P. J. BpCu-
Catalyzed Cyclopropanation of Olefinsꢀ: A Simple System That
Operates under Homogeneous and Heterogeneous Conditions (
Bp ) Dihydridobis ( Pyrazolyl ) Borate ). Organometallics 1998,
7333 (5), 3051–3057.
Burguete, M. I.; Fraile, J. M.; García, J. I.; García-Verdugo, E.;
Herrerías, C. I.; Luis, S. V.; Mayoral, J. A. Bis(Oxazoline)Copper
Complexes Covalently Bonded to Insoluble Support as Catalysts
in Cyclopropanation Reactions. J. Org. Chem. 2001, 66 (26),
8893–8901.
Corma, A.; Iglesias, M.; Llabrés i Xamena, F. X.; Sánchez, F. Cu
and Au Metal-Organic Frameworks Bridge the Gap between
Homogeneous and Heterogeneous Catalysts for Alkene
Cyclopropanation Reactions. Chem. - A Eur. J. 2010, 16 (32),
9789–9795.
(57)
(58)
(59)
(60)
(45)
(46)
For the calculation of the idealized accessible pore diameter,
benzoates were replaced with HO–/H2O.
Wang, B.; Lv, X.-L.; Feng, D.; Xie, L.-H.; Zhang, J.; Li, M.; Xie,
Y.; Li, J.-R.; Zhou, H.-C. Highly Stable Zr(IV)-Based Metal–
Organic Frameworks for the Detection and Removal of
Antibiotics and Organic Explosives in Water. J. Am. Chem. Soc.
2016, 138 (19), 6204–6216.
5
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 6
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
6
ACS Paragon Plus Environment