Article

Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX pubs.acs.org/IC

Cycloaddition of CO2 with an Epoxide-Bearing Oxindole Scaffold by

a Metal−Organic Framework-Based Heterogeneous Catalyst under
Ambient Conditions
Bhavesh Parmar,†,‡,# Parth Patel,§,∥,# Renjith S. Pillai,⊥ Raj Kumar Tak,‡,§
Rukhsana I. Kureshy,‡,§,∥ Noor-ul H. Khan,*,‡,§,∥ and Eringathodi Suresh*,†,‡
†
Analytical and Environmental Science Division and Centralized Instrument Facility and §Inorganic Materials and Catalysis Division,
CSIR-Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar 364 002, Gujarat, India
‡
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201 002, India
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

∥
Charotar University of Science & Technology, Changa, 388 421 Anand, Gujarat, India
⊥
Downloaded via UNIV OF SOUTHERN INDIANA on July 19, 2019 at 13:00:02 (UTC).

Department of Chemistry, Faculty of Engineering and Technology, SRM Institute of Science and Technology, Kattankulathur 603
203, Chennai, India
*
S Supporting Information

ABSTRACT: The synthesis and characterization of a mixed

ligand metal−organic framework (MOF) with good thermal
and chemical stability, {[Co(BDC)(L)·2H 2 O]·xG} n
(CoMOF-2), involving an aromatic dicarboxylate (H2BDC
= 1,4-benzenedicarboxylic acid) and an acyl-decorated N-
donor linker [L = (E)-N′-(pyridin-4-ylmethylene) isonicoti-
nohydrazide] by various physicochemical techniques, includ-
ing Single crystal X-Ray Diffraction (SXRD), are reported.
The MOF showed a good affinity for CO2 capture, and Grand
Canonical Monte Carlo simulation studies exposed strong
interactions of CO2 with the functionalized N-donor ligand of
the framework. CoMOF-2 and KI act as an efficient binary
catalyst for the sustainable utilization of CO2 with spiro-epoxy
oxindole to spirocyclic carbonate under ambient conditions. Notably, herein we report MOF-based catalysis for the
cycloaddition of oxindole-based epoxides with CO2 for harvesting new spirocyclic carbonates. Interestingly, we could isolate and
crystallize six of the spirocyclic carbonate products, and the structure of the newly synthesized molecules has been established
by SXRD analysis. We present a plausible proposed catalytic mechanism through activation of the epoxide ring by the Lewis
acidic/basic sites present on the framework surface that is validated by molecular modeling.

■ INTRODUCTION
Interest in metal−organic frameworks (MOFs), with a porous
nature and good chemical and thermal stability, is rapidly
expanding, and their potential is being exploited in various
applications in the areas of gas storage/separation, sensing,
drug delivery, air purification, etc.1−8 MOFs are attractive
catalytic materials because of their inherent topological and
structural properties, which could be rationally designed by the
sensible choice of the metal nodes and organic linkers.9−12
Nonetheless, the chemical and thermal stability of the pristine
MOF in different solvents, water, and acidic/basic media is a
major concern in practical applications, including cataly-
sis.13−15 A prudent choice of the functionalized ligands as
linkers and metal nodes with a versatile coordination geometry
can govern the porosity, surface area, and stability of the MOF
material with respect to the catalytic application.16,17 Carbon
dioxide (CO2) has attracted more interest recently as a
renewable C1 building block for organic synthesis due to its
abundance, nontoxicity, and environmental issues. One of the
strategies for utilizing CO2 is cycloaddition with epoxides by
developing suitable catalysts for producing value-added
chemicals that have a wide range of applications.18−26
MOFs have attracted interest as a potential heterogeneous
catalyst for the CO2−epoxide cycloaddition reaction based on
their large surface area, tunable pore size, and chemical
stability.27−30 However, MOF-based sustainable catalysis for
CO2 capture and efficient conversion in cycloaddition with
epoxides under ambient conditions into useful organic
pharmaceutical intermediates are limited. The conventional
CO2−epoxide cycloaddition reaction mainly focused on
aromatic/aliphatic epoxide substrates, and heterocyclic epox-
ides have been infrequently explored.31−46 Spirocyclic
compounds with a privileged heterocyclic oxindole motif are
Received: April 26, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.inorgchem.9b01234

Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
widely available in natural alkaloids and recognized as
pharmacologically interesting compounds.47 For example,
oxindole-fused tetrahydropyrane or chroman scaffolds des-
ignated as oxaspirooxindole are notable for their pharmaceut-
ical activities.48−52 Spirocyclic alkaloids spirotryprostatins,
horsfiline and gelsemine, with an oxindole scaffold have
attracted a significant amount of interest of medicinal chemists
because of the presence of the spirotryprostatins in bioactive
natural products.53−56 Due to their biological activity and
physical properties, oxindole or spiro-oxindole core structures
represent an interesting synthetic challenge.57−59 The strategy
for CO2−oxindole epoxide cycloaddition by developing a
suitable catalyst is an innovative way to access spirocyclic
oxindoles. So far, the only synthetic procedure for spirocyclic
oxindole carbonate by CO2−epoxide cycloaddition is reported
on the basis of a deep eutectic solvent.60 Syntheses of organic
molecular architectures with the privileged spiro skeletons
represent a challenge, and these architectures have fascinated
researchers as a class of biologically and pharmaceutically
important compounds.47 The spiro architecture is significantly
biologically important and may render the oxindole carbonate
as an interesting molecule.
The methodology for the assembly of the oxindole core
fused with a cyclic carbonate by CO2 cycloaddition remains
elusive using a MOF-based catalyst. We use the MOF-
catalyzed protocol for the synthesis of spirocyclic oxindole
carbonates facilitating cycloaddition of CO2−oxindole epox-
ides under ambient conditions, significantly improving the
transformation, carbon footprint, and sustainability.
As a continuation of our ongoing research in the area of CO2
utilization,61−64 a microporous three-dimensional (3D) MOF-
based catalytic material, {[Co(BDC)(L)]·2H 2 O·xG} n
(CoMOF-2; G = guest), involving benzene-1,4-dicarboxylic
acid (H2BDC) and N-donor Schiff base ligand L [(E)-N′-
(pyridin-4-ylmethylene) isonicotinohydrazide] with accessible
porosity and densely populated metal sites has been
synthesized by two different approaches and characterized
well by physicochemical methods. Crystals of CoMOF-2 have
been harvested by diffusion, and the phase pure bulk material
has been synthesized by room temperature (RT) stirring of the
constituent ligands with a metal salt. CoMOF-2 possessing
functionally decorated amide group acts as an efficient binary
catalyst for CO2 sequestration/utilization of an oxindole-based
epoxide into a useful oxindole carbonate with mild reaction
parameters. The efficient catalytic activity of CoMOF-2 in
cycloaddition is governed by active Lewis acidic metal sites, the
basic amide functional group on L, and the porosity. The
chemical stability in the solid state or solution, acidic/basic
medium, and the features mentioned above for CoMOF-2
support the excellent catalytic efficiency of this MOF-based
material as a heterogeneous catalyst in oxindole epoxide−CO2
cycloaddition with good yield and recyclability. Preferable
adsorption sites for the CO2 with CoMOF-2 determined by
Grand Canonical Monte Carlo (GCMC) molecular simulation
studies and the possible reaction mechanism for the catalytic
activity have been corroborated by computational methods.
■
EXPERIMENTAL SECTION
Materials and General Methods. All reagents and solvents
purchased from commercial sources were used without further
purification, and synthetic manipulations were performed using
distilled water. The N donor (E)-N′-(pyridin-4-ylmethylene)
isonicotinohydrazide (L) was synthesized according to our previous
B DOI: 10.1021/acs.inorgchem.9b01234
Article
report.65 CHNS analyses were performed using an elementar vario
MICRO CUBE analyzer. Infrared (IR) spectra were recorded using
the KBr pellet method on a Perkin-Elmer GX FTIR spectrometer. For
each IR spectrum, 10 scans were recorded at 4 cm−1 resolution. 1H
and 13C nuclear magnetic resonance (NMR) spectra for the ligand,
epoxides, and cyclic carbonate derivatives were recorded on a JEOL
JNM-ECZ 600R (600 MHz) spectrometer at 25 °C that was
calibrated with respect to internal reference tetramethylsilane.
Thermogravimetric analysis (TGA) was carried out using a Mettler
Toledo Star SW 8.10 instrument. TGA was performed in a nitrogen
environment while the temperature was increased from room
temperature to 700 °C at a rate of 10 °C/min. Powder X-ray
diffraction (PXRD) data were collected using a PANalytical
Empyrean (PIXcel 3D detector) system with Cu Kα radiation.
Single-crystal structures were determined using a BRUKER SMART
APEX (CCD) or BRUKER D8 QUEST (PHOTON) diffractometer.
The N2 and CO2 adsorption−desorption isotherm and BET surface
area were measured on a Micromeritics 3 Flex instrument. Field
emission scanning electron microscopy (FE-SEM) micrographs were
recorded using a JEOL JSM-7100F instrument employing a 15 kV
accelerating voltage.
Synthesis (diffusion method) of {[Co(BDC)(L)·2H2O]·xG}n
(CoMOF-2). H2BDC (benzene-1,4-dicarboxylic acid) (2.5 mmol)
and NaOH (5 mmol) were dissolved in 20 mL to form a clear
solution. N donor linker L (1.25 mmol) was separately solubilized in
20 mL of MeOH. A stock ligand solution was prepared by mixing the
individual linker solution with constant stirring for 15 min and further
diluted to 70 mL with a MeOH/H2O (1:1) mixture. A stock ligand
solution (3 mL) was layered above the 3 mL of the Co(ClO4)2·6H2O
(1 mmol in 15 mL of H2O) solution with 7−8 mL of the buffer
solution (1:1 MeOH:H2O) between them. The test tube was sealed
with parafilm and allowed to stand at room temperature for slow
diffusion for crystallization. X-ray diffraction quality crystals (red in
color) appeared within 1 week. Yield: ∼79%. Elemental analysis (%).
Calcd for {[Co(BDC)(L)·2H2O]·xG}n: C, 45.58; H, 4.74; N, 10.12.
Found: C, 45.54; H, 4.66; N, 10.07. IR (cm−1, KBr): 3385 (w), 3146
(br), 2899 (w), 2842 (w), 1680 (m), 1601 (s), 1554 (s), 1406 (s),
1286 (m), 1139 (w), 1068 (w), 1016 (w), 951 (w), 826 (w), 755 (w),
696 (m), 543 (w).
Bulk Synthesis of CoMOF-2. The bulk powder material of
CoMOF-2 was prepared by stirring a mixture of Co(NO3)2·6H2O
(10 mmol), H2BDC (10 mmol), NaOH (20 mmol), and L (10
mmol) in 100 mL of a mixed solvent [5:4:1 (v:v)
H2O:MeOH:EtOH] for 8 h at room temeperature in a 200 mL
RBF. The resulting precipitate was filtered and washed with a MeOH/
H2O mixture [1:1 (v:v)] and acetone and then air-dried. Yield: ∼92%.
Elemental analysis (%). Calcd for CoMOF-2: C, 45.58; H, 4.74; N,
10.12. Found: C, 45.15; H, 4.83; N, 10.01. FTIR (cm−1, KBr): 3382
(w), 3162 (br), 2899 (w), 2851 (w), 1686 (w), 1625 (m), 1580 (s),
1402 (s), 1290 (m), 1145 (w), 1065 (w), 1017 (w), 946 (w), 833
(w), 750 (w), 694 (m), 533 (w).
Synthetic Procedure for Spiro-Epoxy Oxindole Derivatives.
Spiro-epoxy oxindole derivatives (S1−S8) were synthesized according
to a previous report.66,67 Trimethylsulfoxonium iodide (1.0 mmol)
and CsCO3 (2.0 mmol) were dissolved in dry CH3CN at 50 °C for 1
h under a N2 atmosphere. The N-substituted isatin derivative (1.0
mmol) was dissolved in dry CH3CN (5 mL) and added dropwise over
a 10 min period to the solution described above. Reaction progress
and completion were monitored by thin layer chromatography. The
reaction crude was filtered through a Celite bed and evaporated to
dryness. Column chromatography [silica gel (60−120 mesh), EtOAc/
hexane mixture (20:80) as the eluent] was used to purify the final
product, and it was identified by 1H and 13C NMR spectroscopy.
Crystal structures of S1, S2, S4, S5, and S8 have also been elucidated
using Single crystal X-Ray Diffraction (SXRD).
Synthetic Procedure for Spiro-Epoxy Oxindole−CO2 Cyclo-
addition. Cycloaddition of oxindole epoxide substrates and CO2 was
carried out in a glass tube (5 mL capacity) with constant stirring. For
each reaction, spiro-epoxy oxindole (0.15 mmol), CoMOF-2 (5.0 mol
%), and co-catalyst KI (or TBAI or TBAB; 0.2 mol %), wherever
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 1. (a) PXRD data of CoMOF-2 synthesized by diffusion and RT stirring with simulated SXRD. (b) PXRD data of CoMOF-2 dispersed for
1 week in various organic solvents. (c) PXRD data of CoMOF-2 dispersed in an aqueous acidic/basic solution (0.01 M for 12h). (d) PXRD data of
CoMOF-2 dispersed in boiling water at different temperatures for 24 h.
applicable, were introduced into the glass tube with 1 mL of CH3CN
as the solvent. The glass tube was then pressurized with 1 atm of CO2
at RT. The reaction mixture was heated to the desired temperature
(RT or 40 °C) while being stirred (600 rpm). Upon completion of
the reaction, cycloaddition was stopped and the mixture cooled to
RT. The reaction mixture was then centrifuged to separate the catalyst
and washed with ethyl acetate twice, and the products were isolated
(in ethyl acetate) and identified by gas chromatography using
dodecane as an internal standard [Bruker 450-GC instrument
equipped with an HP-5 capillary column (30 m × 0.25 mm), using
a flame ionization detector]. The cyclic carbonate products were also
identified by 1H and 13C NMR spectroscopy. Crystal structures of
P1−P4, P6, and P8 have also been elucidated using SXRD.
Catalyst Recyclability. Catalyst CoMOF-2 was recovered by
centrifugation after each catalytic reaction, washed with a H2O.MeOH
mixture [1:1 (v:v)] and acetone, air-dried, and used for the next
catalytic reaction under similar conditions for up to six cycles. During
the recyclability study, fresh KI was added during each experiment.
The chemical stability of the recovered catalyst was analyzed by
PXRD, FTIR, and FE-SEM. For recycled CoMOF-2. FTIR (cm−1,
KBr): 3375 (w), 3157 (br), 2899 (w), 2850 (w), 1687 (w), 1624 (m),
1581 (s), 1403 (s), 1290 (s), 1144 (w), 1065 (w), 1017 (w), 946 (w),
833 (w), 750 (w), 698 (m), 538 (w).
■ RESULTS AND DISCUSSION
Characterization and Chemical Stability Study of
CoMOF-2. CoMOF-2 synthesized by different routes
(diffusion and RT stirring) has been characterized with respect
to its thermal and chemical stability and phase purity by
different physicochemical methods such as FTIR, PXRD,
TGA, and FE-SEM. The calculated and measured PXRD data
of the synthesized MOF formed by flexible routes showed
C DOI: 10.1021/acs.inorgchem.9b01234
Article
good agreement, endorsing the phase purity of the material
(Figure 1a).
Symmetric and antisymmetric νCO bands of BDC appeared
at ∼1406 and ∼1554 cm−1, respectively, with a ΔνCO of
∼150 cm−1 indicating chelating/bridging carboxylate coordi-
nation in CoMOF-2. A broad band appeared at 3400−3150
cm−1 in the IR data, indicating vO−H and vN−H vibrations from
water molecules and L (Figure S1). TGA data of CoMOF-2
disclosed good thermal stability, preserving the crystallinity up
to ∼330 °C, and the degradation of the organic moiety
originates after ∼330 °C. TGA of the as-synthesized sample
revealed a weight loss before 120 °C, corresponding to the loss
of lattice water as well as methanol guest molecules, and
structural decomposition commences around 330 °C (Figure
S2). The chemical stability of CoMOF-2 in polar/nonpolar
organic solvents was investigated by soaking the material in the
different solvents for 1 week. PXRD data of the recovered
material from dimethylformamide and dimethyl sulfoxide after
7 days showed a slight variation from the pristine sample,
indicating that the crystallinity and chemical stability
deteriorate with time in these solvents. However, the chemical
stability of the CoMOF-2 recovered from the rest of the
solvents is validated by PXRD data that are in agreement with
those of the pristine sample as shown in Figure 1b.
Furthermore, the stability of CoMOF-2 was systematically
assessed in acidic/basic media by immersion in respective
aqueous solutions (0.01 M for 12 h) at RT. Recovered material
tested by PXRD and FTIR revealed a good match with the
pristine compound representing excellent stability and
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 2. (a) [M2(BDC)2]n 2D sql sheets. (b and c) Double pillaring of 2D sql sheets by L and 2-fold interpenetrated 3D framework in CoMOF-2.
(d) Simplified pcu network topology in CoMOF-2.
retaining the crystallinity and/or structural integrity of the
material in acidic/alkaline media (Figure 1c and Figure S3).
The water stability of CoMOF-2 was evaluated by soaking the
material in water or boiling water at different temperatures and
verified by PXRD and FTIR indicating excellent water stability
(Figure 1d and Figure S3). FE-SEM analysis of synthesized
CoMOF-2 shows a block-shaped morphology for the material
obtained by the diffusion method and an agglomerated
spherical morphology for the bulk material synthesized by
RT stirring and the recovered bulk material after six catalytic
cycles (Figure S4). The concomitant effect of the coordina-
tively saturated Co2 clusters and effective coordination
between the metal centers and the ligand moiety probably
impart excellent thermal and chemical stability on CoMOF-2.
Crystal Structure of CoMOF-2. SXRD data revealed that
CoMOF-2 crystallizes in monoclinic space group C2/c and
features a 3D framework composed of two-dimensional
[M2(BDC)2]n sheets based on dimeric Co(II) carboxylate
clusters, pillared by L. Half of the dimer building block
[Co2(BDC)2(L)2] constitutes the asymmetric unit holding
center of symmetry, which comprises one molecule each of
completely deprotonated BDC and L, crystallographically
independent Co2+, and two water molecules as the solvent of
crystallization.
A distorted octahedral N2O4 geometry around Co(II) is
provided by four carboxylate oxygens from three BDC ligands
creating a distorted square base and pyridyl nitrogen from two
L moieties that completes the axial coordination. Among three
different BDC ligands coordinated to each Co(II), the
carboxylate oxygens are involved in the bridging mode to
D DOI: 10.1021/acs.inorgchem.9b01234
Article
link the dimeric units by two BDC moieties and the third one
yields the chelating mode of coordination.
The [M2(COO)2] secondary building unit (SBU) of the
dimeric cluster is governed by Co2+ nodes linked by syn−syn
coordination from symmetric BDC moieties, which is further
coupled by the chelated carboxylate oxygen from different
BDC ligands creating [M2(BDC)2]n 2D sql sheets (Figure 2a).
Each symmetrically disposed BDC ligand forms a μ3-η1η1η1η1-
chelated bridging mode of coordination with the Co(II),
generating 2D {Co2(BDC)2}n sheets, and the Co(II)···Co(II)
distance across the dimeric unit is 4.11 Å. The edge lengths
between the centers of Co(II) pairs of the square grid window
are 12.69 Å, and the diagonal distance of the {Co2(BDC)2}n
4,4′-net is 17.10 Å. The 2D {Co2(BDC)2}n sheets have an
offset ABAB mode of orientation along the bc plane in which
discrete alternate AAAA as well as BBBB sheets are doubly
pillared via axial coordination by the terminal nitrogen of L
generating an interpenetrated 3D framework (Figure 2b,c).
The 3D framework can be simplified to 6-connected uninodal
nets with pcu topology having a point symbol of {412.63}
(Figure 2d). Hydrogen bonding interaction in CoMOF-2
indicates that the encapsulated water molecules are involved in
strong O−H···O interaction in bridging the interpenetrated 3D
framework (Figure 3 and Table S7).
Gas Adsorption Experimental and Computational
Study. Activated CoMOF-2 (CoMOF-2′) was prepared via
exchange of the reaction solvent with DCM for 24 h, followed
by heating at 120 °C for 12 h in an oven. The permanent
porosity and pore properties of the activated sample of
CoMOF-2′ have been elucidated by gas adsorption isotherms.
N2 (77 K) sorption measurements showed negligible uptake,
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 3. (a) Close-up of H-bonding interaction between two
different nets in CoMOF-2. (b) H-Bonding interaction between two
interpenetrated networks in CoMOF-2.
and the observed BET surface area for CoMOF-2′ was 6.8 m2/
g (Figure S5). The small surface area of CoMOF-2 can be
attributed to the interpenetration of the 3D framework as
depicted in Figure 2c, which in turn can also decrease the
effective porosity. However, adsorption analysis of CO2
revealed promising results, due to the smaller kinetic diameter
of CO2 (3.30 Å) compared to that of N2 (3.64 Å) (Figure 4a).
Pillared linker L from the framework with a polar amide
functional group can interact with CO2 having a high
quadrupole moment. Preferential adsorption of CO2 over N2
can be influenced by the pore size, polarity, or kinetic issue of
the 3D framework.
CO2 adsorption measurements at 273 and 298 K reached
∼51 cm3/g (2.26 mmol/g) and ∼45 cm3/g (2.04 mmol/g),
respectively, at 1 atm, which clearly authenticates the
adsorption capacity of CoMOF-2′ (Figure 4a). Almost
identical CO2 adsorption at 273 and 298 K, despite thermal
agitation at higher temperatures, may be due to the ideal pore
size to fit CO2 and its supramolecular interaction with the
framework. The theoretically predicted small accessible surface
area revealed CoMOF-2′ excludes the N2 due to its kinetic
diameter being larger than the pore size, which is further
endorsed by the experimental surface area (6.8 m2/g) obtained
from the N2 isotherm at 77 K. The adsorption by CoMOF-2′
at 1 atm (2.26 and 2.04 mmol/g at 273 and 298 K,
respectively) is comparable to those of functionally decorated
acylamide/amide MOFs.68−71 Grand Canonical Monte Carlo
E DOI: 10.1021/acs.inorgchem.9b01234
Article
Figure 4. (a) CO2 adsorption isotherm for CoMOF-2′ measured at
273 and 298 K. (b) Local views of the snapshots extracted from the
GCMC simulations for CO2 in CoMOF-2 at 1 bar and 298 K.
(GCMC) simulations fairly reproduce the shape of CO2
adsorption isotherms at 273 and 298 K (Figure S7). To
elucidate the isosteric heat (Qst) for CO2 adsorption in
CoMOF-2′, the Clausius−Clapeyron equation was used from
their corresponding experimental isotherm at 273 and 298 K.
The isosteric heat (Qst) for CO2 reaches ∼35.0 kJ mol−1,
indicating amide functional groups of L may be involved in
strong interactions with the adsorbed CO2 molecules (Figure
S8). In addition, the microscopic mechanism revealed that
CO2 molecules are interacting with the carbonyl group of L,
with mean characteristic O(CO2)−Ocarbonyl distances in the
range of 2.8−3.5 Å (Figure S9) backing the adsorption of CO2
inside the pore (Figure 4b and Figure S10).
Catalytic Performance of CoMOF-2 in Cycloaddition
of Spiro-Epoxy Oxindoles with CO2. The good chemical
and thermal stability, strong CO2 adsorption, functionally
decorated L, and the presence of high-density metal sites are
features required for an excellent catalytic material for CO2−
epoxide cycloaddition. By virtue of these attributes and the
presence of Co(II) with a weakly chelated carboxylate oxygen,
the amide functionality of L in CoMOF-2 can act as a Lewis
acid/basic site in activating the epoxide ring. Unlike a
conventional aromatic/aliphatic epoxide, we have performed
the cycloaddition of CO2 with a series of heterocyclic epoxides
(Scheme 1). A series of spiro-epoxy oxindole substrates have
been synthesized by a reported procedure using trimethylsul-
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

Scheme 1. Cycloaddition of Spiro-Epoxy Oxindole no promising results (Table 1, entries 1−3 and 11−13). For
Derivatives and Carbon Dioxide the best choice of a suitable co-catalyst, reactions were

Table 1. Cycloaddition of 1-Benzylspiro[indoline-3,2′-

oxiran]-2-one (S1) and CO2 for 1-Benzylspiro[indoline-
3,4′-[1,3]dioxolane]-2,2′-dione (P1) Formationa
entry catalyst/co-catalyst temp (°C) time (h) S1 conversion (%)b
1 none RT 24 1
2 CoMOF-2 RT 24 8
foxonium iodide and cesium carbonate at 50 °C in acetonitrile 3 KI RT 24 14
with the respective substituted isatin precursor in quantitative 4 CoMOF-2/TBAB RT 24 52
yield. All of the synthesized spiro-epoxy oxindoles were 5 CoMOF-2/TBAI RT 24 46
characterized by 1H and 13C NMR, and the crystal structures 6 CoMOF-2/KI RT 24 82
of five epoxide derivatives have been established unambigu- 7 CoMOF-2/KI RT 48 85
ously (Figures S11 and S14−S29). Oxindole−epoxide has 8 CoMOF-2/KI 40 24 99
been studied for ring-opening reaction using various 9 CoMOF-2/KI 40 8 99
nucleophiles, and reports of ring expansion are rare.72,73 Ring 10 CoMOF-2/KI 40 6 93
expansion products of oxindole−epoxides by catalytic cyclo- 11 none 40 8 6
addition of CO2 can govern a series of innovative molecules 12 CoMOF-2 40 8 13
that have been infrequently explored, and the spirocyclic 13 KI 40 8 23
oxindole product itself or their derivatives may find significance 14c CoMOF-2D/KI 40 8 97
as intermediates in medicinal chemistry or in the pharmaceut- 15 CoMOF-2/KCl 40 8 82
ical industry. A series of eight spiro-epoxy oxindole substrates a
Reaction conditions: 0.15 mmol of 1S, 600 rpm. Catalyst mole
(S1−S8) with different substitutions have been synthesized percents: 5.0 mol % CoMOF-2 and 0.2 mol % TBAB, TBAI, or KI.
and subjected to cycloaddition with CO2 under a pressure of 1 CH3CN as the solvent. PCO2 = 1 atm. bSelectivity of 99%. cCoMOF-
atm in acetonitrile using CoMOF-2 and a co-catalyst. All 2D indicates the compound was synthesized by the diffusion method.
spirocyclic products were extracted and characterized by gas
chromatography and 1H and 13C NMR spectroscopy, and the
crystal structures of six new spirocyclic products have been performed in the presence of TBAB, TBAI, and KI by retaining
established (Figure 5 and Figures S30−S45). Initially, the initially set up reaction parameters with S1 and co-catalyst
experiments with different parameters were conducted at 1 concentrations 0.15 mmol and 0.2 mol %.
atm of CO2 at RT to optimize the reaction conditions using 1- Excellent results under ambient conditions with 82% S1
benzylspiro[indoline-3,2′-oxiran]-2-one (S1) as the model conversion and 99% product selectivity were achieved for
substrate. A blank reaction and only MOF/KI with the CoMOF-2/KI in a 24 h reaction time, and an only marginal
model substrate revealed minor S1 conversion and upon increase is noticed with an increase in the reaction time to 48 h
variation of the reaction time and/or temperature also yielded (Table 1, entries 6 and 7). With the same reaction parameters,

Figure 5. Thermal ellipsoid plot depicting the crystal structure of spirocyclic carbonates (P1−P4, P6, and P8; 50% probability factor for the
thermal ellipsoids).

F DOI: 10.1021/acs.inorgchem.9b01234
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Table 2. Substrate Screening Using Catalyst CoMOF-2 in the Cycloaddition of Spiro-Epoxy Oxindole CO2a
a
Reaction conditions: 0.15 mmol of epoxide, 5.0 mol % CoMOF-2/0.2 mol % KI as the catalyst, CH3CN as the solvent, PCO2 = 1 atm, 8 h, 40 °C,
600 rpm.
the MOF−co-catalyst (TBAB and TBAI) combinations could
attain only 52% and 46% S1 conversions, respectively (Table 1,
entries 4 and 5, respectively), indicating KI is a more
competent co-catalyst. The initial experiment for screening
the co-catalyst clearly demonstrates the reactivity of KI >
TBAB > TBAI (Table 1, entries 4−6). Due to the bulkiness of
TBAB and TBAI, the diffusion of these co-catalysts toward the
active sites is slower than that of KI, making it the best co-
catalyst in this case. Upon loading KCl as a co-catalyst under
the optimized reaction condition, the epoxide conversion was
82%, comparatively lower than that with KI as a co-catalyst
(Table 1, entry 15). Thus, S1 conversion was only 85% at RT
in 48 h, but when the temperature was increased to 40 °C, 99%
conversion and selectivity were achieved within 24 h (Table 1,
entry 8). If the temperature is held at 40 °C, S1 conversions at
8 and 6 h were 99% and 93%, respectively (Table 1, entries 9
and 10, respectively) and the best solvent system for catalytic
reaction was acetonitrile on the basis of S1 conversion and
selectivity. Reaction parameters for time and temperature were
monitored systematically for CoMOF-2/KI, and the corre-
sponding plots are provided in Figure S12. Catalytic
optimization conducted in various solvents (toluene, methanol,
dichloromethane, acetonitrile, and acetone) is provided in
Table S5. The reactions in solvents proceed with good S1
conversions ranging from 76% to 99% with different product
selectivities. On the basis of solvent optimization experiments,
G DOI: 10.1021/acs.inorgchem.9b01234
Article
the best solvent system for catalytic reaction was acetonitrile
with 99% S1 conversion and selectivity. On the basis of
preliminary systematic screening, the CoMOF-2/KI combina-
tion showed optimized parameters (catalyst/co-catalyst and S1
concentrations of 5.0/0.2 mol % and 0.15 mmol at PCO2 = 1
atm, 40 °C, 8 h, in acetonitrile) for the best catalytic
performance and was used for further catalytic studies. The
catalytic activity of the material synthesized by the diffusion
method under optimized reaction conditions was also
performed to evaluate and compare with the bulk catalytic
material, which showed almost identical results [97% substrate
conversion (Table 1, entry 14)].
We further probed systematically the set of optimal
parameters for cycloaddition of CO2−epoxyindoles (S1−S8)
using binary catalyst CoMOF-2/KI (Table 2). As shown in
Table 2, all substrates undergo catalytic conversion to the
corresponding oxindole spirocyclic carbonates in good yields
(ranging from 75% to 99%).
In the case of N-benzyl spiro-epoxy indole derivatives (S1−
S5), substitution on the aromatic ring (F and CH3) has an only
marginal effect on product yield (Table 2, entries 1−3).
However, substitution with Cl on the aromatic ring decreased
the product yield by 24%, which can be attributed to the bulky
Cl group hindering the accessibility of the reactant and product
toward the active sites by slow diffusion, occurring on the
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 6. Proposed mechanism for CoMOF-2/KI-catalyzed cycloaddition of CO2−spiro-epoxy oxindoles.
surface of the MOF. For the second series (S6−S8), methyl/
allyl substitution on the aromatic/indole nitrogen showed an
only marginal decrease (10% and 8%) for the product
compared to the pristine N-methyl spiro-epoxy oxindole
(Table 2, entries 6−8), and the flexibility of the allyl group
in S8 probably supports the marginal change in the product
yield.
Catalytic Mechanism, Density Functional Theory
(DFT) Calculation, and Recyclability Studies. On the
basis of the literature33,64,74,75 and SXRD analysis, a tentative
reaction mechanism for the catalysis as depicted in Figure 6
has been proposed. Due to the bulkiness of the oxindole
substrate and the reduced effective porosity of the inter-
penetrated framework, the catalytic reaction probably occurs
on the surface of the MOF. The densely populated metal
clusters with a weakly chelated carboxylate group can open and
act as a Lewis acidic site, and a Lewis basic site on ligand L
(−NH of the amide group) can synergistically activate the
epoxide ring (Figure 6). Ma et al. exemplified CO2−epoxide
cycloaddition by MOF-based catalysts bearing both Lewis
acidic and basic sites in the activation of epoxide by a Lewis
H DOI: 10.1021/acs.inorgchem.9b01234
Article
basic catalytic site (−NH− functional group) residing in the
ligand moiety.17 Ligands decorated by Lewis basic sites such as
an amino/acylamide moiety acting as an efficient MOF-based
catalyst for CO2−epoxide cycloaddition are also well
documented in the literature.7,74−76 The basic site favors
CO2 capture in the narrow pores as mentioned above, which is
supported by CO2 adsorption studies and further supple-
mented by molecular modeling experiments in enhancing the
product yield by CO2 conversion.
The plausible mechanism for CoMOF-2/KI-catalyzed
cycloaddition of CO2−spiro-epoxy oxindoles is reinforced by
the DFT calculations (Supporting Information). The energy
profile and mechanistic pathway disclose the synergistic
participation of both the Co(II) metal site and L with the
acyl hydrazine moiety interacting with the epoxides via the
lone pair of oxygen facilitating the ring opening as depicted in
Figure 7. In the catalytic reaction, activation and epoxide ring
opening occur upon coordination of the oxygen from the
epoxide with a Lewis acidic metal. Simultaneously, nucleophilic
attack on the less hindered carbon of epoxides by the iodide
ion (I−) from KI takes place, and the surrounding CO2
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 7. Energy profile diagram for different intermediates and transition states involved in the cycloaddition of spiro-epoxy oxindole and CO2
using the cluster model structure of the CoMOF-2 catalyst with the I− ion.
involved in the reaction generating the alkyl carbonate anion
upon reaction of CO2 with the opened epoxy ring and
subsequent ring closure step with regeneration of the catalyst
engenders the resultant cyclic carbonate. It is worth
mentioning here the mechanism in the cycloaddition of
spiro-epoxy oxindoles with CO2 using DES as an efficient
process reported by Khan et al.60 The hydrogen bond donor
(HBD) and hydrogen bond acceptor (HBA) as a combination
in a 1:2 molar ratio involving urea and choline chloride as a
deep eutectic solvent have shown an excellent efficiency. The
ring opening of epoxide is favored by the synergistic effect of
DES by polarization of the C−O bond of epoxide via H-
bonding followed by nucleophilic attack by Cl. Successively,
the ring-opened intermediate reacts with CO2 and forms the
catalytic product regenerating the DES. For CoMOF-2, both
the Lewis acidic metal site and the basic site from L (acyl
amide functionalized) support activation, opening of the
epoxide ring, and CO2 addition.
The energy profile diagram and the experimental details of
the catalytic reaction mechanism determined by computational
methods are provided in the Supporting Information. As
depicted in Figure 7, the interaction of a cobalt metal center
with the oxygen of the 1-benzylspiro[indoline-3,2′-oxiran]-2-
one (S1) results in an intermediate (Int-1), which is
considered as the initial step in the catalytic pathway, and its
energy is very similar to the sum of the energies of cluster
model of CoMOF-2 (catalyst), a nucleophile (I−), CO2, and
S1 (isolated reactants). At the initial stage, the distance
between the α carbon [αC(epoxide)] of S1 and the I− ion was
>5.5 Å. The approach of the I− ion toward S1 (Int-1)
decreases the relative energy (−2.09 kcal/mol) and the
distance between the cobalt and O atom from S1 (4.06 Å)
as well as that between the α carbon [αC(epoxide)] of S1 and the
I− ion (4.0 Å). During ring opening, nucleophilic attack by the
I DOI: 10.1021/acs.inorgchem.9b01234
Article
iodide ion on the α carbon [αC(epoxide)] of S1 generates an
alkoxide species (IC) with a relative energy (50.9 kcal/mol)
leading to the first transition state (TS-1). The stronger Co−
O(C6) interaction with an interatomic distance of 2.34 Å is
achieved by ring opening of αC(epoxide) followed by the
formation of a new αC(epoxide)−I bond with a distance of 2.57
Å, and the observed relative energy difference between TS-1
and IC is 17.0 kcal/mol.
The rate-determining step is identified as the high-energy
barrier ring opening in CO2 fixation with S1, which is on par
with the previous DFT energy profile. The alkoxide species
with iodide substitution (TS-1) adopts an intermediate state
(Int-2) in the later stage with a total energy value of 30.72
kcal/mol. As indicated in Int-2, the approach of the CO2
molecule at a distance of 2.58 Å and subsequent attack with S1
having a negative charge on oxygen resulted in the formation
of a transition state (TS-2). In the TS-2 step, physical binding
of CO2 between Co and alkoxide takes place via the formation
of new Co−O(CO2) and O(CO2)−αC(epoxide) bonds having
distances of 3.05 and 2.08 Å, respectively, with a relative
energy of 84.5 kcal/mol. In addition, ring closure leads to the
formation of a new intermediate (Int-3) consuming 26.05
kcal/mol. The realization of a new O(epoxide)−C(CO2) bond
leading to the formation of the product 1-benzylspiro[indoline-
3,4′-[1,3]dioxolane]-2,2′-dione (P1) happens in step Int-3 by
the interaction of the carbocation of CO2 with an oxygen atom
of S1. Interestingly, a decrease in the O(CO2)−αC(epoxide) bond
distances is observed (from 1.98 to 1.42 Å), whereas Co−
O(CO2) and C−I distances increase from 3.04 to 4.41 Å and
from 3.14 to 4.07 Å, respectively. The product (P1)
detachment followed by regeneration of the catalyst occurs
with a relative energy of −3.1 kcal/mol in the final step (FC).
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
The isolation of the product, separation, and the recyclability
of the catalyst are important protocols targeting energy
minimization and environmental issues. The catalytic activity
was sustained for up to six repeated cycles, and the chemical
stability and structural integrity of the recycled catalyst were
intact (Figure 8a). The PXRD and FTIR spectra of recycled
Figure 8. (a) Recyclability of CoMOF-2 for up to six catalytic cycles
for S1 conversion. (b) PXRD data of recovered CoMOF-2 after the
sixth cycle for cycloaddition reaction of S1 compared with PXRD data
of the as-synthesized compound.
material showed a pattern identical to that of the pristine
compound (Figure 8b and S1). No enhancement of the
product upon removal of the catalyst clearly demonstrates no
metal leaching and authenticates the active sites reside on the
catalyst (Figure S46).
■
CONCLUSIONS
In summary, a mixed ligand phase pure 3D MOF (CoMOF-2)
with good chemical stability has been synthesized and/or
crystallized by a RT stirring/diffusion method of the precursors
and characterized by different analytical methods. CoMOF-2
has been employed as a recyclable heterogeneous catalyst of
high utility for conversion of a heterocyclic epoxide under mild
reaction condition and utilizing a minimum energy to yield the
corresponding spirocyclic oxindoles efficiently. Spirocyclic
oxindole carbonates are a new series of molecules, and crystal
structures of some of these compounds and substrates have
been determined. The microporosity of CoMOF-2 for CO2
adsorption and Lewis acidic metal and the basic −NH sites in
L facilitate epoxide−CO2 activation and interactions toward
J DOI: 10.1021/acs.inorgchem.9b01234
Article
chemical fixation of CO2 to yield pharmaceutically important
organic spirocyclic oxindoles under ambient conditions. The
mechanism of catalytic reaction is proposed and supported by
DFT calculations. The findings also provide insight for the
synthesis of robust new MOFs utilizing a tailor-made
functionalized ligand with improved catalytic properties in
cycloaddition with sustainable utilization of CO2 and
heterocyclic epoxides producing value-added pharmaceutical
intermediates.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b01234.
Crystallography, computational results, FTIR, TGA, FE-
SEM, N2 isotherm, and NMR spectra (PDF)
Accession Codes
CCDC 1889952−1889962 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: nhkhan@csmcri.res.in.
*E-mail: esuresh@csmcri.res.in or sureshe123@rediffmail.com.
ORCID
Bhavesh Parmar: 0000-0003-4263-7635
Parth Patel: 0000-0001-9742-2784
Renjith S. Pillai: 0000-0003-0165-3305
Raj Kumar Tak: 0000-0003-3726-8687
Rukhsana I. Kureshy: 0000-0001-6611-7605
Noor-ul H. Khan: 0000-0002-5204-5943
Eringathodi Suresh: 0000-0002-1934-6832
Author Contributions
#
B.P. and P.P. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The registration number of this publication is CSIR-CSMCRI-
021/2019. Financial support from CSIR-SRF (BP), DST
Project HCP0009 (PP), and analytical support by AESD&CIF
of CSIR-CSMCRI are gratefully acknowledged. The authors
thank Ms. Pooja Goswami for PXRD, Dr. Vinod Boricha for
NMR data, Mr. Jayesh Chaudhari for FE-SEM analysis, Mr.
Vinod Kumar Agrawal for FTIR data, Mr. Satyaveer Gothwal
for TGA data, Mr. Viral Vakani for CHN analysis, and Mr.
Harpalsinh Rathod for N2/CO2 adsorption−desorption
analysis. R.S.P. thanks the SRM Supercomputer Center, SRM
IST, for providing the computational facility.
■ REFERENCES
(1) Li, J.-R.; Sculley, J.; Zhou, H.-C. Metal-Organic Frameworks for
Separations. Chem. Rev. 2012, 112, 869−932.
(2) He, Y.; Zhou, W.; Qian, G.; Chen, B. Methane storage in metal-
organic frameworks. Chem. Soc. Rev. 2014, 43, 5657−5678.
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
(3) Yu, J.; Xie, L.-H.; Li, J.-R.; Ma, Y.; Seminario, J. M.; Balbuena, P.
B. CO2 Capture and Separations Using MOFs: Computational and
Experimental Studies. Chem. Rev. 2017, 117, 9674−9754.
(4) Adil, K.; Belmabkhout, Y.; Pillai, R. S.; Cadiau, A.; Bhatt, P. M.;
Assen, A. H.; Maurin, G.; Eddaoudi, M. Gas/vapour separation using
ultra-microporous metal-organic frameworks: insights into the
structure/separation relationship. Chem. Soc. Rev. 2017, 46, 3402−
3430.
(5) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne,
R. P.; Hupp, J. T. Metal-Organic Framework Materials as Chemical
Sensors. Chem. Rev. 2012, 112, 1105−1125.
(6) Lustig, W. P.; Mukherjee, S.; Rudd, N. D.; Desai, A. V.; Li, J.;
Ghosh, S. K. Metal-organic frameworks: functional luminescent and
photonic materials for sensing applications. Chem. Soc. Rev. 2017, 46,
3242−3285.
(7) Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.;
Couvreur, P.; Férey, G.; Morris, R. E.; Serre, C. Metal-Organic
Frameworks in Biomedicine. Chem. Rev. 2012, 112, 1232−1268.
(8) DeCoste, J. B.; Peterson, G. W. Metal-Organic Frameworks for
Air Purification of Toxic Chemicals. Chem. Rev. 2014, 114, 5695−
5727.
(9) Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. Commercial
metal-organic frameworks as heterogeneous catalysts. Chem. Commun.
2012, 48, 11275−11288.
(10) Huang, Y.-B.; Liang, J.; Wang, X.-S.; Cao, R. Multifunctional
metal-organic framework catalysts: synergistic catalysis and tandem
reactions. Chem. Soc. Rev. 2017, 46, 126−157.
(11) Dhakshinamoorthy, A.; Asiri, A. M.; Garcia, H. Metal-organic
frameworks catalyzed C-C and C-heteroatom coupling reactions.
Chem. Soc. Rev. 2015, 44, 1922−1947.
(12) Liu, J.; Chen, L.; Cui, H.; Zhang, J.; Zhang, L.; Su, C.-Y.
Applications of metal-organic frameworks in heterogeneous supra-
molecular catalysis. Chem. Soc. Rev. 2014, 43, 6011−6061.
(13) Burtch, N. C.; Jasuja, H.; Walton, K. S. Water Stability and
Adsorption in Metal-Organic Frameworks. Chem. Rev. 2014, 114,
10575−10612.
(14) Emerson, A. J.; Hawes, C. S.; Marshall, M.; Knowles, G. P.;
Chaffee, A. L.; Batten, S. R.; Turner, D. R. High-Connectivity
Approach to a Hydrolytically Stable Metal-Organic Framework for
CO2 Capture from Flue Gas. Chem. Mater. 2018, 30, 6614−6618.
(15) Howarth, A. J.; Liu, Y.; Li, P.; Li, Z.; Wang, T. C.; Hupp, J. T.;
Farha, O. K. Chemical, thermal and mechanical stabilities of metal-
organic frameworks. Nat. Rev. Mater. 2016, 1, 15018.
(16) Yuan, S.; Feng, L.; Wang, K.; Pang, J.; Bosch, M.; Lollar, C.;
Sun, Y.; Qin, J.; Yang, X.; Zhang, P.; Wang, Q.; Zou, L.; Zhang, Y.;
Zhang, L.; Fang, Y.; Li, J.; Zhou, H.-C. Stable Metal-Organic
Frameworks: Design, Synthesis, and Applications. Adv. Mater. 2018,
30, 1704303.
(17) He, H.; Sun, Q.; Gao, W.; Perman, J. A.; Sun, F.; Zhu, G.;
Aguila, B.; Forrest, K.; Space, B.; Ma, S. A Stable Metal-Organic
Framework Featuring a Local Buffer Environment for Carbon Dioxide
Fixation. Angew. Chem., Int. Ed. 2018, 57, 4657−4662.
(18) Aresta, M.; Dibenedetto, A.; Angelini, A. Catalysis for the
Valorization of Exhaust Carbon: from CO2 to Chemicals, Materials,
and Fuels. Technological Use of CO2. Chem. Rev. 2014, 114, 1709−
1742.
(19) Markewitz, P.; Kuckshinrichs, W.; Leitner, W.; Linssen, J.;
Zapp, P.; Bongartz, R.; Schreiber, A.; Müller, T. E. Worldwide
innovations in the development of carbon capture technologies and
the utilization of CO2. Energy Environ. Sci. 2012, 5, 7281−7305.
(20) Rokicki, G.; Parzuchowski, P. G.; Mazurek, M. Non-isocyanate
polyurethanes: synthesis, properties, and applications. Polym. Adv.
Technol. 2015, 26, 707−761.
(21) Yang, L.-C.; Rong, Z.-Q.; Wang, Y.-N.; Tan, Z. Y.; Wang, M.;
Zhao, Y. Construction of Nine-Membered Heterocycles through
Palladium-Catalyzed Formal [5 + 4] Cycloaddition. Angew. Chem., Int.
Ed. 2017, 56, 2927−2931.
(22) Cai, A.; Guo, W.; Martínez-Rodríguez, L.; Kleij, A. W.
Palladium-Catalyzed Regio-and Enantioselective Synthesis of Allylic
K DOI: 10.1021/acs.inorgchem.9b01234
Article
Amines Featuring Tetrasubstituted Tertiary Carbons. J. Am. Chem.
Soc. 2016, 138, 14194−14197.
(23) Ninokata, R.; Yamahira, T.; Onodera, G.; Kimura, M. Nickel-
Catalyzed CO2 Rearrangement of Enol Metal Carbonates for the
Efficient Synthesis of β-Ketocarboxylic Acids. Angew. Chem., Int. Ed.
2017, 56, 208−211.
(24) Guo, W.; Gónzalez-Fabra, J.; Bandeira, N. A. G.; Bo, C.; Kleij,
A. W. A Metal-Free Synthesis of N-Aryl Carbamates under Ambient
Conditions. Angew. Chem., Int. Ed. 2015, 54, 11686−11690.
(25) Schäffner, B.; Schäffner, F.; Verevkin, S. P.; Börner, A. Organic
Carbonates as Solvents in Synthesis and Catalysis. Chem. Rev. 2010,
110, 4554−4581.
(26) Vivek, J. P.; Berry, N.; Papageorgiou, G.; Nichols, R. J.;
Hardwick, L. J. Mechanistic Insight into the Superoxide Induced Ring
Opening in Propylene Carbonate Based Electrolytes using in Situ
Surface-Enhanced Infrared Spectroscopy. J. Am. Chem. Soc. 2016, 138,
3745−3751.
(27) He, H.; Perman, J. A.; Zhu, G.; Ma, S. Metal-Organic
Frameworks for CO2 Chemical Transformations. Small 2016, 12,
6309−6324.
(28) Maina, J. W.; Pozo-Gonzalo, C.; Kong, L.; Schütz, J.; Hill, M.;
Dumée, L. F. Metal organic framework based catalysts for CO2
conversion. Mater. Horiz. 2017, 4, 345−361.
(29) Trickett, C. A.; Helal, A.; Al-Maythalony, B. A.; Yamani, Z. H.;
Cordova, K. E.; Yaghi, O. M. The chemistry of metal-organic
frameworks for CO2 capture, regeneration and conversion. Nat. Rev.
Mater. 2017, 2, 17045.
(30) Sharma, N.; Dhankhar, S. S.; Nagaraja, C. M. A Mn(II)-
porphyrin based metal-organic framework (MOF) for visible-light-
assisted cycloaddition of carbon dioxide with epoxides. Microporous
Mesoporous Mater. 2019, 280, 372−378.
(31) Guillerm, V.; Weseliński, L. J.; Belmabkhout, Y.; Cairns, A. J.;
D’Elia, V.; Wojtas, L.; Adil, K.; Eddaoudi, M. Discovery and
introduction of a (3,18)-connected net as an ideal blueprint for the
design of metal-organic frameworks. Nat. Chem. 2014, 6, 673−680.
(32) Feng, D.; Chung, W.-C.; Wei, Z.; Gu, Z.-Y.; Jiang, H.-L.; Chen,
Y.-P.; Darensbourg, D. J.; Zhou, H.-C. Construction of Ultrastable
Porphyrin Zr Metal-Organic Frameworks through Linker Elimination.
J. Am. Chem. Soc. 2013, 135, 17105−17110.
(33) Gao, W.-Y.; Chen, Y.; Niu, Y.; Williams, K.; Cash, L.; Perez, P.
J.; Wojtas, L.; Cai, J.; Chen, Y.-S.; Ma, S. Crystal Engineering of an
nbo Topology Metal-Organic Framework for Chemical Fixation of
CO2 under Ambient Conditions. Angew. Chem., Int. Ed. 2014, 53,
2615−2619.
(34) Beyzavi, M. H.; Klet, R. C.; Tussupbayev, S.; Borycz, J.;
Vermeulen, N. A.; Cramer, C. J.; Stoddart, J. F.; Hupp, J. T.; Farha, O.
K. A Hafnium-Based Metal-Organic Framework as an Efficient and
Multifunctional Catalyst for Facile CO2 Fixation and Regioselective
and Enantioretentive Epoxide Activation. J. Am. Chem. Soc. 2014, 136,
15861−15864.
(35) Alkordi, M. H.; Weseliński, L. J.; D’Elia, V.; Barman, S.; Cadiau,
A.; Hedhili, M. N.; Cairns, A. J.; AbdulHalim, R. G.; Basset, J.-M.;
Eddaoudi, M. CO2 conversion: the potential of porous-organic
polymers (POPs) for catalytic CO2-epoxide insertion. J. Mater. Chem.
A 2016, 4, 7453−7460.
(36) Kathalikkattil, A. C.; Babu, R.; Roshan, R. K.; Lee, H.; Kim, H.;
Tharun, J.; Suresh, E.; Park, D.-W. An lcy-topology amino acid MOF
as eco-friendly catalyst for cyclic carbonate synthesis from CO2:
Structure-DFT corroborated study. J. Mater. Chem. A 2015, 3,
22636−22647.
(37) Aguila, B.; Sun, Q.; Wang, X.; O’Rourke, E.; Al-Enizi, A. M.;
Nafady, A.; Ma, S. Lower Activation Energy for Catalytic Reactions
through Host-Guest Cooperation within Metal-Organic Frameworks.
Angew. Chem., Int. Ed. 2018, 57, 10107−10111.
(38) Zhou, Z.; He, C.; Xiu, J.; Yang, L.; Duan, C. Metal-Organic
Polymers Containing Discrete Single-Walled Nanotube as a
Heterogeneous Catalyst for the Cycloaddition of Carbon Dioxide to
Epoxides. J. Am. Chem. Soc. 2015, 137, 15066−15069.
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
(39) Kurisingal, J. F.; Rachuri, Y.; Pillai, R. S.; Gu, Y.; Choe, Y.; Park,
D.-W. Ionic liquid-functionalized UiO-66 framework: An experimen-
tal and theoretical study on the cycloaddition of CO2 and epoxide.
ChemSusChem 2019, 12, 1033−1042.
(40) Nguyen, P. T. K.; Nguyen, H. T. D.; Nguyen, H. N.; Trickett,
C. A.; Ton, Q. T.; Gutiérrez-Puebla, E.; Monge, M. A.; Cordova, K.
E.; Gándara, F. New Metal-Organic Frameworks for Chemical
Fixation of CO2. ACS Appl. Mater. Interfaces 2018, 10, 733−744.
(41) Ding, M.; Jiang, H.-L. Incorporation of Imidazolium-Based
Poly(ionic liquid)s into a Metal-Organic Framework for CO2 Capture
and Conversion. ACS Catal. 2018, 8, 3194−3201.
(42) De, D.; Pal, T. K.; Neogi, S.; Senthilkumar, S.; Das, D.; Gupta,
S. S.; Bharadwaj, P. K. A Versatile CuII Metal-Organic Framework
Exhibiting High Gas Storage Capacity with Selectivity for CO2:
Conversion of CO2 to Cyclic Carbonate and Other Catalytic Abilities.
Chem. - Eur. J. 2016, 22, 3387−3396.
(43) Subramanian, S.; Park, J.; Byun, J.; Jung, Y.; Yavuz, C. T. Highly
Efficient Catalytic Cyclic Carbonate Formation by Pyridyl Salicyli-
mines. ACS Appl. Mater. Interfaces 2018, 10, 9478−9484.
(44) Ugale, B.; Kumar, S.; Dhilip Kumar, T. J.; Nagaraja, C. M.
Environmentally Friendly, Co-catalyst-Free Chemical Fixation of CO2
at Mild Conditions Using Dual-Walled Nitrogen-Rich Three-Dimen-
sional Porous Metal-Organic Frameworks. Inorg. Chem. 2019, 58,
3925−3936.
(45) Yue, S.; Wang, P.; Hao, X. Synthesis of cyclic carbonate from
CO2 and epoxide using bifunctional imidazolium ionic liquid under
mild conditions. Fuel 2019, 251, 233−241.
(46) Sun, Y.; Huang, H.; Vardhan, H.; Aguila, B.; Zhong, C.;
Perman, J. A.; Al-Enizi, A. M.; Nafady, A.; Ma, S. Facile Approach to
Graft Ionic Liquid into MOF for Improving the Efficiency of CO2
Chemical Fixation. ACS Appl. Mater. Interfaces 2018, 10, 27124−
27130.
(47) Singh, G. S.; Desta, Z. Y. Isatins As Privileged Molecules in
Design and Synthesis of Spiro-Fused Cyclic Frameworks. Chem. Rev.
2012, 112, 6104−6155.
(48) Yu, B.; Yu, D.-Q.; Liu, H.-M. Spirooxindoles: Promising
scaffolds for anticancer agents. Eur. J. Med. Chem. 2015, 97, 673−698.
(49) Zhou, R.; Wu, Q.; Guo, M.; Huang, W.; He, X.; Yang, L.; Peng,
F.; He, G.; Han, B. Organocatalytic cascade reaction for the
asymmetric synthesis of novel chroman-fused spirooxindoles that
potently inhibit cancer cell proliferation. Chem. Commun. 2015, 51,
13113−13116.
(50) Zhang, M.; Fu, Q.-Y.; Gao, G.; He, H.-Y.; Zhang, Y.; Wu, Y.-S.;
Zhang, Z.-H. Catalyst-Free, Visible-Light Promoted One-Pot Syn-
thesis of Spirooxindole-Pyran Derivatives in Aqueous Ethyl Lactate.
ACS Sustainable Chem. Eng. 2017, 5, 6175−6182.
(51) Mao, H.; Lin, A.; Tang, Y.; Shi, Y.; Hu, H.; Cheng, Y.; Zhu, C.
Organocatalytic oxa/aza-Michael-Michael Cascade Strategy for the
Construction of Spiro [Chroman/Tetrahydroquinoline-3,3′-oxindole]
Scaffolds. Org. Lett. 2013, 15, 4062−4065.
(52) Kouznetsov, V. V.; Merchan Arenas, D. R.; Arvelo, F.; Forero, J.
S. B.; Sojo, F.; Munoz, A. 4-Hydroxy-3-methoxyphenyl Substituted 3-
methyl-tetrahydroquinoline Derivatives Obtained Through Imino
Diels-Alder Reactions as Potential Antitumoral Agents. Lett. Drug
Des. Discovery 2010, 7, 632−639.
(53) Ramakumar, K.; Maji, T.; Partridge, J. J.; Tunge, J. A. Synthesis
of Spirooxindoles via the tert-Amino Effect. Org. Lett. 2017, 19,
4014−4017.
(54) Galliford, C. V.; Scheidt, K. A. Pyrrolidinyl-Spirooxindole
Natural Products as Inspirations for the Development of Potential
Therapeutic Agents. Angew. Chem., Int. Ed. 2007, 46, 8748−8758.
(55) Marti, C.; Carreira, E. M. Construction of Spiro[pyrrolidine-
3,3′-oxindoles] - Recent Applications to the Synthesis of Oxindole
Alkaloids. Eur. J. Org. Chem. 2003, 2003, 2209−2219.
(56) Zhu, G.; Bao, G.; Li, Y.; Sun, W.; Li, J.; Hong, L.; Wang, R.
Efficient Catalytic Kinetic Resolution of Spiro-epoxyoxindoles with
Concomitant Asymmetric Friedel-Crafts Alkylation of Indoles. Angew.
Chem., Int. Ed. 2017, 56, 5332−5335.
L DOI: 10.1021/acs.inorgchem.9b01234
Article
(57) Antonchick, A. P.; Gerding-Reimers, C.; Catarinella, M.;
Schürmann, M.; Preut, H.; Ziegler, S.; Rauh, D.; Waldmann, H.
Highly enantioselective synthesis and cellular evaluation of spiroox-
indoles inspired by natural products. Nat. Chem. 2010, 2, 735−740.
(58) Vintonyak, V. V.; Warburg, K.; Kruse, H.; Grimme, S.; Hübel,
K.; Rauh, D.; Waldmann, H. Identification of Thiazolidinones Spiro-
Fused to Indolin-2-ones as Potent and Selective Inhibitors of the
Mycobacterium tuberculosis Protein Tyrosine Phosphatase B. Angew.
Chem., Int. Ed. 2010, 49, 5902−5905.
(59) Tak, R. K.; Gupta, N.; Kumar, M.; Kureshy, R. I.; Khan, N. H.;
Suresh, E. Regioselective Alcoholysis and Hydrochlorination Reac-
tions of Spiro-Epoxy Oxindoles at the Spiro-Centre: Synthesis of 3,3-
Disubstituted Oxindoles and Application for Anticancer Agents. Eur.
J. Org. Chem. 2018, 2018, 5678−5687.
(60) Tak, R. K.; Patel, P.; Subramanian, S.; Kureshy, R. I.; Khan, N.
H. Cycloaddition Reaction of Spiro-Epoxy Oxindole with CO2 at
Atmospheric Pressure Using Deep Eutectic Solvent. ACS Sustainable
Chem. Eng. 2018, 6, 11200−11205.
(61) Patel, P.; Parmar, B.; Kureshy, R. I.; Khan, N. H.; Suresh, E.
Efficient Solvent-Free Carbon Dioxide Fixation Reactions with
Epoxides Under Mild Conditions by Mixed-Ligand Zinc(II) Metal-
Organic Frameworks. ChemCatChem 2018, 10, 2401−2408.
(62) Patel, P.; Parmar, B.; Kureshy, R. I.; Khan, N. H.; Suresh, E.
Amine-functionalized Zn(II) MOF as an efficient multifunctional
catalyst for CO2 utilization and sulfoxidation reaction. Dalton Trans.
2018, 47, 8041−8051.
(63) Parmar, B.; Patel, P.; Kureshy, R. I.; Khan, N. H.; Suresh, E.
Sustainable Heterogeneous Catalysts for CO2 Utilization by Using
Dual Ligand ZnII/CdII Metal-Organic Frameworks. Chem. - Eur. J.
2018, 24, 15831−15839.
(64) Parmar, B.; Patel, P.; Pillai, R. S.; Kureshy, R. I.; Khan, N. H.;
Suresh, E. Efficient Catalytic Conversion of Terminal/ Internal
Epoxides to Cyclic Carbonates by Porous Co(II) MOF at Ambient
Conditions: Structure Property Correlation and Computational
Studies. J. Mater. Chem. A 2019, 7, 2884−2894.
(65) Parmar, B.; Rachuri, Y.; Bisht, K. K.; Suresh, E. Syntheses and
Structural Analyses of New 3D Isostructural Zn(II) and Cd(II)
Luminescent MOFs and their Application Towards Detection of
Nitroaromatics in Aqueous Media. Chemistry Select 2016, 1, 6308−
6315.
(66) Chouhan, M.; Senwar, K. R.; Sharma, R.; Grover, V.; Nair, V.
A. Regiospecific epoxide opening: a facile approach for the synthesis
of 3-hydroxy-3-aminomethylindolin-2-one derivatives. Green Chem.
2011, 13, 2553−2560.
(67) Tak, R. K.; Gupta, N.; Kumar, M.; Kureshy, R. I.; Khan, N. H.;
Suresh, E. Regioselective Alcoholysis and Hydrochlorination Reac-
tions of Spiro-Epoxy Oxindoles at the Spiro-Centre: Synthesis of 3,3-
Disubstituted Oxindoles and Application for Anticancer Agents. Eur.
J. Org. Chem. 2018, 2018, 5678−5687.
(68) Zheng, B.; Bai, J.; Duan, J.; Wojtas, L.; Zaworotko, M. J.
Enhanced CO2 Binding Affinity of a High-Uptake rht-Type Metal-
Organic Framework Decorated with Acylamide Groups. J. Am. Chem.
Soc. 2011, 133, 748−751.
(69) Roztocki, K.; Jȩdrzejowski, D.; Hodorowicz, M.; Senkovska, I.;
Kaskel, S.; Matoga, D. Isophthalate-Hydrazone 2D Zinc-Organic
Framework: Crystal Structure, Selective Adsorption, and Tuning of
Mechanochemical Synthetic Conditions. Inorg. Chem. 2016, 55,
9663−9670.
(70) Stylianou, K. C.; Warren, J. E.; Chong, S. Y.; Rabone, J.; Bacsa,
J.; Bradshaw, D.; Rosseinsky, M. J. CO2 selectivity of a 1D
microporous adenine-based metal-organic framework synthesised in
water. Chem. Commun. 2011, 47, 3389−3391.
(71) Chen, M.; Chen, S.; Chen, W.; Lucier, B. E. G.; Zhang, Y.;
Zheng, A.; Huang, Y. Analyzing Gas Adsorption in an Amide-
Functionalized Metal Organic Framework: Are the Carbonyl or
Amine Groups Responsible? Chem. Mater. 2018, 30, 3613−3617.
(72) Hajra, S.; Maity, S.; Roy, S. Regioselective Friedel-Crafts
Reaction of Electron-Rich Benzenoid Arenes and Spiroepoxyoxindole
at the Spiro-Centre: Efficient Synthesis of Benzofuroindolines and
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

2H- Spiro[benzofuran]-3,3′-oxindoles. Adv. Synth. Catal. 2016, 358,

2300−2306.
(73) Jiang, H.; Jie, H.; Li, J. Scandium triflate-catalyzed selective ring
opening and rearrangement reaction of spiro-epoxyoxindole and
carbonyl compounds. RSC Adv. 2016, 6, 100307−100311.
(74) Kim, J.; Kim, S.-N.; Jang, H.-G.; Seo, G.; Ahn, W.-S. CO2
cycloaddition of styrene oxide over MOF catalysts. Appl. Catal., A
2013, 453, 175−180.
(75) Li, P.-Z.; Wang, X.-J.; Liu, J.; Phang, H. S.; Li, Y.; Zhao, Y.
Highly Effective Carbon Fixation via Catalytic Conversion of CO2 by
an Acylamide-Containing Metal-Organic Framework. Chem. Mater.
2017, 29, 9256−9261.
(76) Guo, X.; Zhou, Z.; Chen, C.; Bai, J.; He, C.; Duan, C. New rht-
Type Metal-Organic Frameworks Decorated with Acylamide Groups
for Efficient Carbon Dioxide Capture and Chemical Fixation from
Raw Power Plant Flue Gas. ACS Appl. Mater. Interfaces 2016, 8,
31746−31756.

M DOI: 10.1021/acs.inorgchem.9b01234
Inorg. Chem. XXXX, XXX, XXX−XXX