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Chemistry—A European Journal doi.org/10.1002/chem.202002996
& Polyhedral Silsesquioxanes
Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro-Site
Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and
Low-Pressure CO2
Mateusz Janeta,* Tadeusz Lis, and Sławomir Szafert*[a]
Abstract: In the present research, the synthesis, spectro-
scopic characterization, and structural investigations of a
unique ZnII complex of imine-functionalized polyhedral oli-
gomeric silsesquioxane (POSS) is designed, and hereby de-
scribed, as a catalyst for the synthesis of cyclic carbonates
from epoxides and CO2. The uncommon features of the de-
signed catalytic system is the elimination of the need for a
high pressure of CO2 and the significant shortening of reac-
tion times commonly associated with such difficult transfor-
mations like that of styrene oxide to styrene carbonate. Our
studies have shown that imine-POSS is able to chelate metal
Introduction
Polyhedral silsesquioxanes, organosilicon compounds de-
scribed by the chemical formula (RSiO3/2)n, are representatives
of a class of cage-like compounds.[1–3] Polyhedral oligomeric sil-
sesquioxane (POSS) cages include usually T6, T8, T10, and T12,
structures, however, the most widely studied are the cubic T8
as well as, recently, the lantern,[4] butterfly,[5] Janus,[6] or double-
decker[7] types of cages. On the basis of their diameters, which
range from 1 to 3 nm, they can be considered as the smallest
existing silica nanoparticles. Their unique star-shaped nano-
structures make POSS an excellent building block for con-
structing of multi-functional materials.[8, 9] The advantage of
POSS lies in its wide range of interesting physicochemical pa-
rameters, that is, facile chemical modification, good pH toler-
ance, high temperature and oxidation stability, mechanical re-
sistance, optical transparency, reduced heat transfer coefficient,
resistance to fire, and hardness of silsesquioxane-based materi-
als.
Recently, in the field of silsesquioxanes, we have observed
an increased interest in POSS-based systems, which could
serve as homogeneous catalysts. Such systems generally con-
[a] Dr. M. Janeta, Prof. T. Lis, Prof. S. Szafert
Faculty of Chemistry
University of Wrocław
F. Joliot-Curie 14, 50-383 Wrocław (Poland)
E-mail: mateusz.janeta@chem.uni.wroc.pl
slawomir.szafert@chem.uni.wroc.pl
Supporting information and the ORCID identification number(s) for the au-
thor(s) of this article can be found under:
https://doi.org/10.1002/chem.202002996.
Chem. Eur. J. 2020, 26, 13686 – 13697
ions like ZnII to form a unique coordination complex. The sil-
sesquioxane core and the hindrance of the side arms (their
steric effect) influence the construction process of the ho-
moleptic Zn4@POSS-1 complex. The compound was charac-
terized in solution by NMR (1H, 13C, 29Si), ESI-MS, UV/Vis spec-
troscopy and in the solid state by thermogravimetric/differ-
ential thermal analysis (TG-DTA), elemental analysis, diffuse
reflectance infrared Fourier transform spectroscopy (DRIFTS),
cross-polarization magic angle spinning (CP MAS) NMR (13C,
29
Si) spectroscopy, and X-ray crystallography.
sist of a metalated T7 moiety, R7Si7O12M (where M = a d-block
element; R = an isobutyl or cyclopentyl group), often with ad-
ditional ligands coordinated to the metal site (Figure 1 a).[10–14]
For example, Duchateau et al. described the preparation of ZnII
alkyl silsesquioxane complexes for the co-polymerization of cy-
clohexene oxide and CO2.[15] Zirconium(IV) silsesquioxane com-
plexes have been investigated as model catalysts for alkene
polymerization and the same research group has also prepared
similar SnII, AlIII, and GaIII species.[16–18] Silsesquioxanes contain-
ing Si-O-M (where M = zirconium,[19] titanium,[20] or iron[21]) con-
nections have been studied as molecular models for heteroge-
neous catalysis.
More recently, this interest has expanded to encompass oc-
tahedral systems. T8 compounds containing metals may be di-
vided into two groups: (1) those with a metal ion directly
bonded to the silsesquioxane core (mostly via an oxygen or sil-
icon atom, Figure 1 b) and (2) those with seven inert organic
substituents and a single metalated site on one outside arm of
the cube (Figure 1 c).
As said already, the metal sites in metal-silsesquioxane can
act as catalytic centers. A rare example of a crystallographically
characterized metalated silsesquioxane-based catalytic system
is that of Maschmeyer et al., who have used silsesquioxanes as
soluble models for tethered OsIV and RhII complexes.[25, 26] Also,
Ervithayasuporn et al.[24] reported a mononuclear organopalla-
dium-functionalized T8-Pd POSS as a homogeneous catalyst for
the Suzuki–Miyaura reaction (Figure 1 c). Marciniec et al. de-
scribed a ruthenium-silsesquioxyl complex active in silylative
coupling reactions (Figure 1 b).[22] Jones et al. synthesized and
structurally characterized AlIII[23] and ZnII[27] POSS complexes
and reported on their activity in the ring-opening polymeri-
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Chemistry—A European Journal doi.org/10.1002/chem.202002996

Cyclic carbonates are characterized by a range of applica-

tions, for instance: monomers for polymerization, substrates in
organic synthesis, green solvents, or electrolytes for lithium-ion
batteries.[48, 49] From the above reasons, a number of research
groups have focused their attention on the preparation of effi-
cient catalytic systems for cyclic carbonate synthesis including
metal complexes with imine,[50–54] aminophenolate,[55, 56] por-
phyrin,[57, 58] or other ligands.[59–62] Also, an organocatalytic ap-
proach has actively been investigated.[63–65]
It is also known that the cooperative effects of two or more
metal sites in salphen complexes play an important role in sev-
eral catalytic reactions. Therefore, efforts have been made to
synthesize molecular structures with multiple salphen/salen
binding pockets, creating a potential for placement of two or
more catalytically active metal centers in a predefined three-di-
Figure 1. Selected types of silsesquioxane complexes: a) T7 system, b) T8 mensional geometry.[66]
system with a metal ion directly bonded to the silsesquioxane core, c) sys- Over the last two decades, the North group has developed
tems with seven inert organic substituents and a single metalated site on aluminium-based salen complexes as highly effective catalysts
one outside arm of the cube.[21–24]
for the synthesis of cyclic carbonates from epoxides and
carbon dioxide.[67–69] Their studies resulted in the development
zation of rac-lactide. Grela et al.[28] reported a ruthenium POSS of a bimetallic complex (Figure 2 b), which was shown to be a
complex active in Hoveyda–Grubbs-type olefin metathesis, more efficient catalyst for the formation of cyclic carbonates
which can be recovered by using nanofiltration techniques. from epoxides than the monometallic aluminium(salphen)
Other types of catalytically active mononuclear silsesquioxane complexes.[70] The same group has also developed silica-sup-
metal complexes include a zirconium-functionalized POSS, re- ported catalysts with propylene oxide, which are reusable over
ported by Severn et al., which acts as a homogeneous model 30 times and could convert up to 98 % of CO2 into ethylene
for silica-supported olefin polymerization catalysts.[29] carbonate with use of a flow reactor.[71] Kleij et al.[72] has report-
To date, metal complexes of silsesquioxanes are created ed several Zn(salphen) complexes as effective, cheap, robust,
through either the introduction of metal ions by post-function- and relatively green catalysts for the cycloaddition of carbon
alization[30, 31] or the use of predefined metalated ligand build- dioxide to terminal epoxides to afford cyclic carbonates in
ing blocks as reactants.[32] To the best of our knowledge, there
is no example in the literature of a well-defined (structurally
characterized) T8-POSS that coordinates more than one metal
cation using side arms.[33]
On the other hand, carbon dioxide is a well-known green-
house gas that originates from the carbon footprint of human
activities and the natural carbon cycle.[34–36] Neutralization of
CO2 is of great significance for the deceleration of global
warming and the development of sustainable energy. One, and
a potentially long-term, solution to balance these emissions is
permanent CO2 trapping into minerals;[37–41] however, this
method requires considerable costs and energy. Recent prog-
ress in coordination chemistry and catalysis could provide an
effective means for the chemical transformation of CO2 and its
longer-term incorporation into organic molecules under mild
conditions.[42, 43] In this regard, much attention has been paid
to the synthesis of cyclic carbonates or polycarbonates from
epoxides and CO2 (Scheme 1) owing to the their useful proper-
ties.[44–47]

Figure 2. Selected complexes that are effective catalysts for the synthesis of
cyclic carbonates from epoxides and carbon dioxide: a) monometallic zinc-
(salphen) complexes,[72] b) bimetallic aluminium(salphen),[70] c) trimetallic
Scheme 1. Reaction between CO2 and epoxides. R can be H, alkyl, or aryl. metal-salen molecular cages.[48]

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Chemistry—A European Journal doi.org/10.1002/chem.202002996
good yields (Figure 2 a). Wu et al.[48] described AlIII and CoIII
salen based molecular cages, which have proven to be efficient
and recyclable heterogeneous catalysts for cycloaddition of
CO2 with epoxides under ambient conditions.
Inspired by these reports, we designed, and hereby describe,
the synthesis, characterization, and structural investigations of
a new ZnII complex with polyhedral oligomeric silsesquioxane
as a catalyst for the synthesis of cyclic carbonates from epox-
ides and CO2. This search relates to the industry search for a
thermally stable systems that would allow the process to be
conducted at low CO2 pressures. According to this, we envi-
sioned POSS as perfect carriers for anchoring of a metal that is
active in cyclic carbonates formation.
Imine-POSS comprises a less-explored group of modified
POSSs. Our previous studies demonstrated that imine-POSS are
a versatile precursor for building supramolecular hybrid materi-
als.[73] Synthesis of well-defined metal complexes of POSS is
challenging and to date, efficient methods for their prepara-
tion have been lacking. At the same time, no papers have de-
scribed the chemistry or the synthetic aspects of metal com-
plexes of imino-octafunctionalized POSS (so-called multifunc-
tional POSS). It was interesting to determine whether such
POSS moieties can play the role of multifunctional ligands ca-
pable of anchoring more than just one metal center.
Results and Discussion
Synthesis
A zinc(II) complex with Schiff base attached POSS was conven-
iently prepared in two steps. First, octa-iminofunctionalized
POSS derivative POSS-1 was obtained in high yield, by using
octa(3-aminopropyl)silsesquioxane (OAS-POSS), 3,5-di-tert-
butyl-2-hydroxybenzaldehyde, and triethylamine as a deproto-
nation agent as shown in Scheme 2. The reaction was conduct-
ed at room temperature in a mixture of CH2Cl2/methanol (v/v,
1:5) resulting in 91 % of POSS-1.
The new imino-functionalized POSS-1 was characterized by
NMR (1H, 13C, 29Si), DRIFT spectroscopy, and ESI-MS spectrome-
try (Figures S3–S8 in the Supporting Information). In solution,
it possesses Oh symmetry, manifested in its NMR (1H, 13C) spec-
tra by a set of symmetry-equivalent signals of organic side
Scheme 2. Synthesis of POSS-1.
Chem. Eur. J. 2020, 26, 13686 – 13697 www.chemeurj.org 13688
chains. In the 1H NMR spectrum, only one characteristic signal
of the imine group proton at d = 8.33 ppm was observed and
the phenol OH signal was located at 13.95 ppm. Moreover, the
presence of the iminopropyl group (-N = CH) was evidenced
by a single resonance at 158.4 ppm in the 13C NMR spectrum.
The mass spectrum also unambiguously confirmed the forma-
tion of a closed-frame structure composed of eight silicon
atoms possessing terminal alkyl-imine side chains showing a
signal at m/z = 2610.4979 (calcd 2610.4984) with a correct iso-
tope envelope. In the diffuse reflectance infrared Fourier trans-
form (DRIFT) spectrum of POSS-1, a sharp band appeared at
1636 cm@1, which was attributed to the nC=N stretching vibra-
tions of the imine group. Owing to an intramolecularly hydro-
gen-bonded OH group, the nO-H vibrations displayed a band in
the 3100–2500 cm@1 region. Also, the Si-O-Si stretching gave
rise to strong absorptions at around 1116 cm@1.
Metalation of POSS-1 with zinc(II) acetate in a mixture of di-
chloromethane and methanol (v/v, 1:1) yielded a tetranuclear
coordination compound Zn4@POSS-1 (Scheme 3). The complex
was also successfully synthesized in high yield by a one-step
protocol using ZnEt2 in toluene and POSS-1 with a precise 4:1
molar ratio under dinitrogen at @78 8C. When POSS-1 was re-
acted with an excess (5–8 equivalents) of diethylzinc to obtain
compounds with higher (than four) numbers of coordinated
zinc(II) ions, we invariably observed only the formation of
Zn4@POSS-1. Recrystallization of Zn4@POSS-1 from CHCl3 led
to isolation of an analytically pure product, which was charac-
terized by NMR spectroscopy and mass spectrometry (see the
Experimental Section and Figures S9–S18 in the Supporting In-
formation). It should be noted that Zn4@POSS-1 is stable
under ambient conditions and can be stored for several weeks
without any signs of degradation.
The formation of Zn4@POSS-1 was confirmed by 1H NMR
spectroscopy, which, in CDCl3, showed two sets of resonances
assigned to the phenyl ring and two assigned to the diastereo-
topic -CH2- protons associated with iminopropyl functional
groups arising from the ligand. Compared with the spectra of
the pure ligand, the lower chemical shifts observed for the
CH = N (at 8.17 and 8.10 ppm) moiety and the absence of the
broad OH signal suggested its coordination through the imine
and phenoxo groups, indicating a lower symmetry than that of
POSS-1. In the DRIFT spectrum of Zn4@POSS-1, new bands,
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Chemistry—A European Journal doi.org/10.1002/chem.202002996
Scheme 3. Preparation of Zn4@POSS-1.
which were absent in the spectra of the free ligand, were ob-
served at 1531 and 1434 cm@1; these were attributed to the co-
ordinated nC-O mode. Bands at 539 and 517 cm@1 were as-
signed to the Zn@O and Zn@N bonds, respectively. The nC=N
band was shifted to 1613 cm@1, whereas the nO-H stretching vi-
brations disappeared, indicating that the ligand was coordinat-
ed in its phenol-imine form. In the DRIFT spectrum, no
CH3COO@ moieties were observed, proving that the ZnII ions
were connected by imine ligands only. This result was in agree-
ment with the NMR spectroscopy observations (see above).
Characteristic vibrations of the Si-O-Si moieties were observed
at 1097 cm@1. The absence of Si-OH group absorptions sup-
ported the preservation of the cage-like structure,[73] which
was further supported by our observations from solution and
solid-state 29Si NMR analysis (see below). Tetranuclear stoichi-
ometry with the formula Zn4@POSS-1 was confirmed with the
ESI-MS spectrum of the isolated complex, which showed ad-
ducts with protons [Zn4@POSS-1 + 2 H]2 + (Figure S18 in the
Supporting Information). Elemental analyses were also consis-
tent with the proposed formulations. Importantly, the POSS
cage did not react with either ZnEt2 or Zn(CH3COO)2 and did
not decompose during the complexation reaction.
To further confirm our observations, we acquired 13C and 29Si
NMR spectra in solution and in the solid state. The 29Si NMR
spectrum of Zn4@POSS-1 in solution (Figure S11 in the Sup-
porting Information) contained only one resonance at
@66.8 ppm, which means that cage rearrangement did not
occur. In addition, the 29Si cross-polarization magic angle spin-
ning (CP MAS) spectrum (Figure S16 in the Supporting Infor-
mation) recorded for a bulk sample also showed only one sym-
metric resonance at @66.8 ppm. Thus, these results unambigu-
ously confirmed that only a T8 cage is present in the resulting
structure.
Imine-POSS in which two side-chain iminopropyl group are
connected through a metal atom, can form one of the two iso-
Chem. Eur. J. 2020, 26, 13686 – 13697 www.chemeurj.org 13689
mers with D4h or S4 symmetry (Figure 3). D4h symmetry of
Zn4@POSS-1 was authenticated by NMR and single-crystal X-
ray diffraction studies as indicated below.
Figure 3. Schematic representation of the two possible connections of side
arms of imine-POSS.
X-ray analysis
A single crystal of Zn4@POSS-1 suitable for X-ray diffraction
analysis was obtained by slow evaporation of a chloroform so-
lution of the complex. Zn4@POSS-1 crystallizes in a monoclinic
system in C2/c space group. The X-ray structure of Zn4@POSS-
1 is shown in Figure 4 and in Figure S1 (in the Supporting In-
formation). The solid-state structure revealed the formation of
a neutral four-coordinate tetranuclear complex. Each metal
center is ligated by two imine nitrogens and two phenolate
oxygens of two neighboring iminophenolate side arms of
POSS-1. Each side arm plays the role of a ligand in a bidentate
(k2) fashion. Zinc(II) ions adopt a distorted tetrahedral geome-
try. Two zinc atoms have a configuration D and the other two
L, resulting in an overall D4h molecule symmetry of meso-
(D,D,L,L)-Zn4@POSS-1. Owing to steric hindrance by the tert-
butyl groups, rotation around the Zn atom is blocked, which
prevents Zn4@POSS-1 from isomerization (Figure 4, Figure 5 a).
Zn@O bond lengths are in the 1.914(5)–1.924(4) a range and
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Chemistry—A European Journal doi.org/10.1002/chem.202002996

Figure 4. X-ray crystal structure of Zn4@POSS-1 (left). Hydrogen atoms and chloroform molecules have been omitted for clarity. View of the coordination envi-
ronments of the zinc center (right) in Zn4@POSS-1. Symmetry code: i3/2@x, 3/2@y, 1@z.

Figure 5. X-ray crystal structure of Zn4@POSS-1·10 CHCl3 : a) view of a chloroform molecule trapped in the cavity created by the side group of Zn4@POSS-1,
b) space-filling representation, c) surface plot of the pores formed by the arrangement of solvent molecules lying among Zn4@POSS-1 molecules. Representa-
tion of channels along the b-axis. The image shows a 1.5 V 1.5 V 1.5 array of unit cells.

Zn@N bonds in the 1.979(6)–2.016(5) a range, typical for ZnII
Schiff base complexes, for which Zn@O and Zn@N bond
lengths fall within the ranges of 1.890–2.139 a and 1.980–
2.128 a, respectively.[74] The Si@O distances in the centrosym-
metric molecule fell within the range 1.611(5)–1.633(5) a. The
Si atoms tended to maintain tetrahedral geometry, with O-Si-O
angles ranging from 107.8(2) to 109.9(2)8, however, the Si@O@
Si bond angles, strained by the cuboidal geometry imposed by
the Si atoms, widened to 139.6(3)–167.3(3)8, representing a sig-
nificant deviation from the ideal oxygen bond angle of 1048
(for more details, see the Supporting Information, Table S2 and
Figure S1, and the CIF file). Nevertheless, all values concerning
the core fell within the standard range for T8-like silsesquiox-
anes.[73]
Analysis of the crystal structure revealed that supramolecular
aggregation in Zn4@POSS-1 occurred through weak coopera-
tive noncovalent interactions CH2···H3C (2.146 a, @10.6 % below
the sum of van der Waals radii), CH3···H3C (2.313 a, @3.63 %
< vdW sum), Si···HC (3.149 a, @4.58 % < vdW sum) to produce
an extended 3D network. Data on the geometry of the hydro-
gen bonds and the close noncovalent contacts are presented
in Table S3 and in Figure S2 (in the Supporting Information).
Zn4@POSS-1 co-crystallized with ten chloroform molecules,
which were trapped between the side arms of Zn4@POSS-1
and connected by C@H···p and C@H···O interactions (Figure 5 a),
creating an interconnected torus-like aggregate. The volume
of chloroform molecules (contact surface) in a Zn4@POSS-1
crystal was estimated at 32.3 % of the unit cell volume
(19 683 a3 per unit cell), with a solvent-accessible pore volume
of 7.6 % (1489 a3 per unit cell; Figure 5 b, c). Zn4@POSS-1
indeed appears to be a possible host for host/guest materials.
Compounds that possess noncovalent interactions may serve
as molecular containers for small molecules with potential uses
in so-called green reactions, in which selective trapping of a
specific small molecules from a reaction system is a key per-
formance of the molecular reactor.

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Chemistry—A European Journal doi.org/10.1002/chem.202002996
Thermal properties
The inorganic framework (Si-O-Si) ensures the chemical and
thermal resistance of the POSS compounds. Compared with
pure organic compounds, hybrid organic–silsesquioxanes are
characterized by a much higher thermal stability. To character-
ize the thermal stability of POSS-1 and Zn4@POSS-1, a thermal
gravimetric analysis (TGA) was carried out in an oxidative (O2/
N2 = 40:60) and anaerobic (nitrogen flow) environment. The
TGA profiles are presented in Figure 6 (oxidative environment)
and Figure S19 (nitrogen flow; in the Supporting Information).
The TGA curve of POSS-1 indicated its high thermal stability
up to 346 (nitrogen flow) and 321 8C (oxidative environment),
which can be attributed to the presence of the rigid silses-
quioxane cage.[75] Oxidative decomposition of POSS-1 occurred
in two main steps. The first weight loss was related to a de-
composition of organic side chains and the second to that of
the siloxane cage. Continuation of the analyses up to 1000 8C
under oxidative conditions enabled determination of the mate-
rials composition based on their ceramic yields.[75] The final
product of thermooxidative degradation was silicon oxide in
crystobalite form (ICSD number: 75483), as confirmed by X-ray
powder diffraction. The TGA curve of POSS-1 revealed a total
weight loss of 81.8 %, corresponding to 18.2 % of remaining
SiO2, which is close to the theoretical value (18.4 %).
Figure 6. TGA trace graph (in an oxidative environment) for POSS-1 and
Zn4@POSS-1. Theoretical values of weight loss are given in parentheses.
For Zn4@POSS-1, the initial weight loss of 3 % was related to
the release of the remaining solvent molecules trapped be-
tween the side arms. The thermal behavior of Zn4@POSS-1 fol-
lowing desolvation was similar to that for POSS-1, with a more
important mass loss occurring in the second step as a result of
decomposition of the organic arms (first step for POSS-1). The
TGA results show that the thermal stability of desolvated
Zn4@POSS-1 at the 5 % weight reduction temperature (DT5 %)
reached 346 8C under the nitrogen flow and 334 8C in an oxida-
tive environment. The total weight loss of 75.7 % was close to
the theoretical value of 74.1 % calculated for Zn4Si8O16.
Chem. Eur. J. 2020, 26, 13686 – 13697 www.chemeurj.org
UV/Vis absorption
The UV/Vis absorption spectra for POSS-1 and Zn4@POSS-1
were investigated in CH2Cl2 solutions at a concentration of
10@7 mol L@1 (Figure 7) and the corresponding data are com-
piled in the Experimental Section. The UV/Vis spectrum of
POSS-1 showed three bands; p!p* transitions of the C=N
groups are in the range 290–375 nm, whereas the bands in the
ranges 220–250 and 250–280 nm may be attributed to p!p*
and n!p* transitions of the aromatic rings. The UV/Vis spec-
trum of Zn4@POSS-1 displays an absorption pattern similar to
that of the ligand, but bathochromically shifted. The large
(compared with that observed for free Schiff base POSS-1) red-
shift can be assigned to the reduction of the transition energy
levels owing to a high degree of electron density on the Schiff
base ligand.[76]
Figure 7. The electronic absorption spectra (in dichloromethane) for POSS-1
(black) and Zn4@POSS-1 (red).
Catalytic test using Zn4@POSS-1 for the coupling of CO2
with epoxides
The effects of the nature of the co-catalyst, catalyst/co-catalyst
ratio, solvent, and temperature were examined by using sty-
rene oxide as the model substrate. The initial conditions were
1 atm CO2, 100 8C, 1 mol % of catalyst, and 1 equivalent of TBAI
(relative to Zn), as a co-catalyst in neat substrate for 4 h. The
results are summarized in Table 1. Under these conditions, no
catalytic activity was observed when using Zn4@POSS-1 alone
(Table 1, entry 1). A control experiment without Zn4@POSS-1
catalyst resulted in negligible conversion of styrene oxide
(Table 1, entry 2).
The optimal catalyst center/co-catalyst ratio was 1:1, as no
improvement was achieved if the ratio was increased to 1:2
(Table 1, entry 7). An increase in temperature from 100 to
130 8C resulted in a higher conversion (98 %, turnover frequen-
cy (TOF) = 56 h@1, Table 1, entry 11), whereas at 80 8C a de-
crease in activity was observed (45 %, TOF = 10 h@1, Table 1,
entry 3). When the catalyst loading of Zn4@POSS-1 was re-
duced to 0.1 mol %, the conversion of styrene oxide to styrene
carbonate decreased to 49 % (Table 1, entry 8). A longer reac-
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and leaving group ability of iodide compared with bromide,

Table 1. Optimization of reaction conditions for the cycloaddition of sty-
rene oxide and CO2.[a] which enhanced the ring-opening and -closing catalytic
steps.[77]
To investigate the mechanism involved in the synthesis of
cyclic carbonate, a study of the reaction kinetics was per-
formed by using [D7]DMF as a solvent. Reaction progress was
observed with real-time NMR spectra. The conversion of sty-
rene oxide and the resulting yield increased along with in-
Entry Cat. Co-cat. Temp. [8C] Time [h] Conversion [%][b]
creasing reaction times, from 0 to 4 h (Figure 8). After 1 h (at
100 8C), more than 40 % of the substrates were converted and
1 Zn4@POSS-1 – 100 4 0
2 – TBAI 100 4 1
a styrene carbonate yield of 60 % was detected. Full conversion
3 Zn4@POSS-1 TBAI 80 4 45 of styrene oxide was achieved with the reaction time of 4 h
4 Zn4@POSS-1 TBAI (0.25)[c] 100 4 85 (Figure 8). For the conversion of styrene oxide with 1 atm CO2
5 Zn4@POSS-1 TBAI (0.5)[c] 100 4 90 pressure at three different temperatures (80 8C, 100 8C, and
6 Zn4@POSS-1 TBAI 100 4 96
7 Zn4@POSS-1 TBAI (2)[c] 100 4 96
130 8C), first-order kinetics were observed.
8 Zn4@POSS-1[d] TBAI 100 4 49 To investigate if the zinc(II) centers in Zn4@POSS-1 function
9 Zn4@POSS-1[d] TBAI 100 12 95 separately or cooperatively, we used the method described by
10 Zn4@POSS-1 TBAI 100 10 96 North et al.,[70] which is based on the investigation of the effect
11 Zn4@POSS-1 TBAI 130 4 98
of changing the metal active center/TBAX ratio (X can be Cl,
[a] Reaction conditions: styrene oxide (4.4 mmol), catalyst (44 mmol, Br, or I). If they function separately, then one equivalent of
1 mol %), co-catalyst (4 mol %, 1 equiv rel. to Zn), CO2 (1 atm). [b] Deter-
TBAX per metal center will be required, whereas if they func-
mined by using 1H NMR spectroscopy. [c] Number in brackets is the
equivalents per Zn. [d] Reaction conditions: styrene oxide (4.4 mmol), cat- tion cooperatively then less than one equivalent of TBAX per
alyst (4.4 mmol, 0.1 mol %), co-catalyst (0.4 mol %, 1 equiv rel. to Zn), CO2 metal will be needed. In the case of Zn4@POSS-1, using sty-
(1 atm). rene epoxide at 100 8C and 1 atm carbon dioxide pressure for
4 h, 96 % conversion was obtained when using 1 mol % of
Zn4@POSS-1 and 1 equiv (rel. to Zn) of TBAI whilst 90 % con-
tion time (12 instead of 4 h) at this reduced catalyst loading al- version was obtained when using 1 mol % of Zn4@POSS-1 and
lowed us to achieve 95 % conversion (Table 1, entry 9). 0.5 equiv (rel. to Zn) of TBAI. Further reduction of the amount
The influence of the co-catalyst was also investigated and of TBAI to 0.25 equiv (rel. to Zn) resulted in a reduction of the
the results are summarized in Table 2. It is well known that the conversion to 85 %, which may indicate that zinc atoms work
nucleophilicity and leaving group ability of the co-catalyst can cooperatively. These results are consistent with a mechanism
determine its activity.[69] N-Methylimidazole (NMI) and 4-dime- that was previously proposed for aluminium(salphen) com-
thylaminopyridine (DMAP) were weak co-catalysts as only 5 % plexes[70] in which one metal center activates the epoxide
and 8 % conversions were observed after 4 h (Table 2, entries 1 while the other activates the carbon dioxide to allow intramo-
and 2). When tetrabutylammonium fluoride (TBAF), chloride lecular carbonate formation. A possible mechanism for the
(TBACl), or tetrabutylammonium bromide (TBAB) were used as
a co-catalysts, low conversions and TOFs were also observed
(Table 2, entries 3–5). However, when tetrabutylammonium
iodide (TBAI) was used (Table 2, entry 6), an increase in conver-
sion up to 96 % (TOF = 25 h@1) was noticed. The higher activity
observed for iodide (96 %) compared with bromide (40 %) and
other halogens can be related to the higher nucleophilicity

Table 2. Influence of co-catalyst on the catalytic activity of Zn4@POSS-

1.[a]

Entry Co-cat. TOF [h@1][b] Conversion [%][c]

1 NMI 1.25 5
2 DMAP 2 8
3 TBAF 1.5 6
4 TBACl 2.5 10
5 TBAB 10 40
6 TBAI 25 96 Figure 8. Kinetic profiles for the formation of styrene carbonate from styrene
oxide and CO2 at different reaction temperatures when using the
[a] Reaction conditions: styrene oxide (4.4 mmol), Zn4@POSS-1 (44 mmol,
Zn4@POSS-1/TBAI system. Reaction conditions: substrate (0.22 mmol), cata-
1 mol %), co-catalyst (4 mol %, 1 equiv rel. to Zn), CO2 (1 atm), 100 8C, 4 h.
lyst Zn4@POSS-1 (1 mol %), CO2 (1 atm), co-catalyst TBAI (4 mol %, 1 equiv
[b] TOF = moles of product/(moles of active site of catalyst V time) at
rel. to Zn), solvent [D7]DMF (0.6 mL). The solid line represents the fit with
10 % conversion. [c] Determined by using 1H NMR spectroscopy.
the pseudo-first-order kinetic model.

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 Full Paper
Chemistry—A European Journal doi.org/10.1002/chem.202002996
Scheme 4. Proposed cooperative mechanism for cyclic carbonate synthesis catalyzed by the Zn4@POSS-1/TBAI system.
conversion of styrene oxide by Zn4@POSS-1/TBAI is shown in
Scheme 4. First, the zinc-salen acts as a Lewis acid to coordi-
nate styrene oxide to activate the epoxide ring (polarizes it) for
nucleophilic attack from the iodine anion from TBAI. Simulta-
neously, the tetrabutylammonium iodide molecule forms tribu-
tylamine,[78] which reacts reversibly with CO2 to create a carba-
mate salt. The polymetallic nature of Zn4@POSS-1 allows it to
coordinate to carbamate. Displacement of the tributylammoni-
um group generates the metal-coordinated carbonate and
subsequent ring-closure forms the cyclic carbonate and regen-
erates both Zn4@POSS-1 and tetrabutylammonium iodide.
The proposed mechanism emphasizes that the role of the
catalyst involves initial activation of the epoxide and stabiliza-
tion of its ring-opened form (iodo-alkoxide) and carbonate in-
termediates formed during the reaction, which is important to
reduce the reaction pressure of CO2 and the reaction time. The
catalytic performance depends on the nucleophilicity and leav-
ing group properties of the halide, as well as the stabilizing
effect of the counterion. Moreover, the in situ formation of tri-
alkylamine followed by the formation of a carbamate salt with
CO2 was considered to play an additional catalytic role in this
process.[68]
To further study the cooperative nature of the catalyst, we
compared the obtained results with those for monometallic
zinc(salen)[79] (Figure 9). When 4 mol % of compound 1 and
1 equiv TBAI were used as the catalyst, at 1 atm of CO2 and
100 8C, after 4 h only 60 % conversion of styrene oxide into
cyclic carbonate was observed. Even when the reaction tem-
Figure 9. Bis(salicylaldimine) zinc(II) complex Zn4@POSS-1 counterpart.[79]
Chem. Eur. J. 2020, 26, 13686 – 13697 www.chemeurj.org
perature was raised to 130 8C, the conversion only increased to
70 %. Thus, higher conversion (96 %) of styrene carbonate was
obtained with tetrametallic Zn4@POSS-1 than with the mono-
metallic analog 1 (60 %) under the same reaction conditions,
supporting the occurrence of intramolecular cooperative catal-
ysis with Zn4@POSS-1.
The recyclability of Zn4@POSS-1 was finally evaluated.
Zn4@POSS-1 retained most of its catalytic activity even after
five runs, with the conversions decreasing from 99 % to 90 %
(Figure 10). The NMR spectra of Zn4@POSS-1 after the catalytic
reaction was the same as before, which may indicate that the
molecular structure is preserved. Mass spectrometry data con-
firm that Zn4@POSS-1 retains its tetrametallic structure during
reactions and after its use in five consecutive reactions. More-
over, the inductively coupled plasma optical emission spectros-
copy (ICP-OES) analysis of the reaction mixture after filtering
showed only a trace amount (below 8 ppm) of zinc atoms, in-
dicating negligible leaching of Zn into the reaction mixture.
Figure 10. Reaction conditions: styrene oxide (0.22 mmol), catalyst
(2.2 mmol, 1 mol %), co-catalyst (4 mol %, 1 equiv rel. to Zn), CO2 (1 atm),
T = 100 8C, no solvent, 4 h.
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Chemistry—A European Journal doi.org/10.1002/chem.202002996
Substrate scope
We next investigated the scope and limitations of the
Zn4@POSS-1/TBAI system for a variety of terminal and internal
epoxides, which included: 1-chloro-2,3-epoxypropane, 1,2-ep-
oxyethylbenzene, 1,2-epoxybutane, 1,2-epoxycyclohexane, 1,2-
epoxypropane, 1,2-epoxyhexane, and 1,2-epoxy-3-phenoxypro-
pane (Figure 11). The influence of the substrate was explored
at a reaction temperature of 100 8C in the presence of
Zn4@POSS-1 and TBAI under a pressure of 1 atm CO2. To deter-
mine isolated yields, the mixture after reaction was purified by
means of flash chromatography (using a mixture of hexane/
EtOAc). For all studied epoxides, formation of cyclic carbonate
was unambiguously confirmed by NMR spectroscopy (Figur-
es S20–S31 in the Supporting Information), which confirmed
the high selectivity of the catalytic system and an absence of
polycarbonate or hydrolysis products. Industrially, the most
challenging substrate for cyclic carbonate synthesis is styrene
oxide owing to its lower reactivity and selectivity.[80, 81] In the
case of the Zn4@POSS-1/TBAI system, high yields (85–99 %) of
cyclic carbonates were achieved under mild conditions for ter-
minal epoxides, illustrating that this catalytic system was effec-
tive with both alkyl and aryl epoxides, tolerating functional
groups such as halides and ethers (Figure 11). The modest
yields of propylene and butylene carbonate were due to the
high volatility of propylene and butylene oxide even at room
temperature. An internal epoxide, cyclohexene oxide, was con-
verted into the corresponding cyclic carbonate with 5 % yield.
Even using TBAB as a co-catalyst did not increase the yield sig-
nificantly (7 % yield). The reduction of activity was in this case
caused by the steric hindrance induced by the silsesquioxane
substituents. X-ray crystallography showed that Zn4@POSS-1 is
characterized by large structural elements (silsesquioxane core)
erected over the active site region, allowing substrate access
only through a deep, narrow channel. This architecture ac-
counts for the tendency of the described catalyst to specialize
in small substrates without bulky groups and to maintain the
reaction at the stage of formation of cyclic carbonate. The side
arms of Zn4@POSS-1 form cavities that are large enough (12 a
in diameter) to accommodate small molecules, which has been
Figure 11. Isolated yields of cyclic carbonates formed by the cycloaddition
of CO2 with epoxides catalyzed by Zn4@POSS-1. Reaction conditions: sub-
strate (4.4 mmol), Zn4@POSS-1 (1 %), TBAI (4 mol %, 1 equiv rel. to Zn), CO2
(1 atm), T = 100 8C, no solvent, 4 h.
Chem. Eur. J. 2020, 26, 13686 – 13697 www.chemeurj.org
confirmed with X-ray analysis (see above). The distance be-
tween two zinc atoms is 11 a and is close enough for coopera-
tive interactions to take place between them. The metallic
center is more easily accessible to terminal epoxides. The fact
that low conversion was observed for internal epoxides like cy-
clohexene oxide can suggest that the reaction occurs inside
the cavities.
The activity of the Zn4@POSS-1/TBAI system is significant
compared with the most efficient amino- or imino-phenolate
complexes reported heretofore (based on Zn,[82, 83] Al,[84]
Mn,[72, 85] Fe,[86] Co,[87, 88] and Cr[89, 90]), which usually operate in
the presence of CO2 under high pressure (up to 30 bar), with
catalyst loadings of 0.01–6.6 mol %, and which require a pro-
longed reaction time (up to 48 h).[72] For example, for mononu-
clear Zn(salphen), the efficiency after 18 h (under 10 mbar CO2)
is 66 %.[72] Moreover, we investigated new applications of
imine-POSS in catalysis with a green approach, preferring the
use of relatively nontoxic metals such as zinc and avoiding the
use of solvents that exert a negative impact on the environ-
ment.
Conclusion
A new type of tetranuclear ZnII coordination compound was
designed and synthesized utilizing a reaction of ZnII ions with
imine-functionalized polyhedral silsesquioxane. For the first
time, a multifunctional imine-POSS-based metal complex was
structurally characterized. Zn4@POSS-1 was obtained in high
yields through simultaneous complexation reactions of imine-
functionalized silsesquioxane with ZnII salts under mild condi-
tions. Zn4@POSS-1 was successfully tested in the cycloaddition
of CO2 with terminal epoxides, with tetrabutylammonium
iodide as a co-catalyst, which ensured a high activity and selec-
tivity of the tested catalytic system. Styrene oxide, which is
usually a challenging substrate, was converted under mild con-
ditions (1 atm CO2) and with a short reaction time (4 h) into
the corresponding cyclic carbonate, in high yield (96 %). For
terminal epoxides, high yields (85–99 %) of cyclic carbonates
were achieved under mild conditions, illustrating that this cata-
lytic system was effective with both alkyl and aryl epoxides
while tolerating functionalities including halides and ethers.
Experimental Section
General procedures and chemicals
Dichloromethane (99 %, Chempur), chloroform (99 %, Chempur),
methanol (99 %, Chempur), 3,5-di-tert-butyl-2-hydroxybenzalde-
hyde (99.9 %, Aldrich), 1-chloro-2,3-epoxypropane (99 %, Acros),
1,2-epoxybutane (99 %, Sigma–Aldrich), 1,2-epoxycyclohexane
(98 %, EGA-chem), 1,2-epoxyethylbenzene (97 %, Sigma–Aldrich),
1,2-epoxyhexane (97 %, Acros), 1,2-epoxy-3-phenoxypropane (99 %,
Acros), 1,2-epoxypropane (+ 99.5, Sigma–Aldrich), tetrabutylammo-
nium bromide (99 %, Lancaster), tetrabutylammonium chloride
(99 %, Acros), tetrabutylammonium fluoride (99 %, Sigma–Aldrich),
tetrabutylammonium iodide (99 %, Sigma–Aldrich), triethylamine
(99.5 %, Aldrich), N-methylimidazole (99 %, Sigma–Aldrich), 4-dime-
thylaminopyridine (98 %, Acros), 1,3,5-trimethylbenzene (99 %,
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Chemistry—A European Journal doi.org/10.1002/chem.202002996
Sigma–Aldrich), zinc(II) acetate (99.9 %, Alfa Aesar), ZnEt2 (1.0 m so-
lution in hexanes, Aldrich) were used as received. Toluene was puri-
fied and dried by using a solvent-purification system that con-
tained activated alumina. Octa(3-aminopropyl)silsesquioxane hy-
drochloride[91] and 1,2-ethanediamino-N,N’-bis(3,5-di-tert-butylsali-
cylidene) zinc(II)[79] were prepared with a method based on a previ-
ously reported procedure. CO2 used for the catalytic tests was
technical grade and was obtained from Linde Gaz Polska.
Synthesis
POSS-1: 3,5-Di-tert-butyl-2-hydroxybenzaldehyde (0.799 g,
3.41 mmol, 8.0 equiv) was added dropwise to a suspension of
octa(3-aminopropyl)silsesquioxane hydrochloride (0.500 g,
0.426 mmol), triethylamine (0.475 mL, 0.345 g, 3.41 mmol,
8.0 equiv), and MgSO4 (0.050 g) in a mixture of methanol (50 mL)
and chloroform (10 mL). The resulting suspension was stirred for
24 h at room temperature. After that time, the solvent was evapo-
rated. The crude product was purified by washing with water (3 V
20 mL), then with methanol (3 V 10 mL), and after that it was dried
in vacuo (25 8C, 0.5 mbar) to give the expected product in 91 %
yield (1.010 g, 0.387 mmol) as a yellow solid. 1H NMR (500 MHz,
CDCl3, 300 K): d = 13.95 (s, 8 H, OH), 8.33 (s, 8 H, CHN), 7.35 (d,
4
JHH = 2.3 Hz, 8 H, 6-Ph), 7.06 (d, 4JHH = 2.4 Hz, 8 H, 4-Ph), 3.55 (t,
3
JHH = 6.5 Hz, 16 H, CH2N), 1.84–1.78 (m, 16 H, -CH2-), 1.43 (s, 72 H,
tBu), 1.28 (s, 72 H, tBu) 0.71 ppm (t, 3JHH = 8.4 Hz, 16 H, SiCH2);
13 1
C{ H} NMR (126 MHz, CDCl3, 300 K): d = 166.0 (Ph-OH), 158.4 (C=
N), 139.9 (3-Ph), 136.7 (5-Ph), 126.8 (4-Ph), 125.9 (6-Ph), 118.0 (1-
Ph), 62.0 (CH2N), 35.2 (CMe3), 34.2 (CMe3), 31.7 (-(CH3)3), 29.6
(-(CH3)3), 24.6 (CH2), 9.7 ppm (SiCH2); 29Si{1H} NMR (59.6 MHz, CDCl3,
300 K): d = @66.6 (s); DRIFT: ṽ = 3100–2500 (m, nO-H), 2954 (s, nC-H),
2908 (m, nC-H), 2866 (m, nC-H), 1636 (s, nC=N), 1471 (m, dC-O), 1361 (m,
nC-N), 1249 (m, nC-O), 1116 cm@1 (s, nSi-O-Si); HRMS (ESI + , TOF), m/z:
2610.4979 [M+ +H] + (calcd 2610.4984), 1305.7700 [M+ +2 H]2 + (calcd
1305.7528), 870.8397 [M+ 3+
+3 H] (calcd 870.8376); elemental analy-
sis calcd (%) for C144H224N8O20Si8 (2612.05): C 66.21, H 8.64, N 4.29;
found: C 66.36, H 8.83, N 4.21; UV/Vis (dichloromethane, 293 K) l
(log e): 231 (6.49), 262 (6.27), 328 nm (5.83 m@1 cm@1); decomposi-
tion onset temperature (DTG, 10 8C min@1): 321 8C (air), 346 8C (N2);
temperature of decomposition to SiO2 (determined by TGA mea-
surement, air, 10 8C min@1): 633 8C, residue yield: 18.23 % (calcd
18.40 %).
Zn4@POSS-1: Method A. Zn(CH3COO)2 (0.281 g, 1.531 mmol,
4.0 equiv), POSS-1 (1.0 g, 0.383 mmol), and a mixture of dichloro-
methane (20 mL) and methanol (20 mL) were stirred for 24 h at
room temperature. Subsequently, the solvent was evaporated. The
resulting yellow solid was recrystallized from chloroform at @15 8C
to yield 60 % (0.658 g, 0.230 mmol) Zn4@POSS-1. Single crystals
were grown by means of a slow-evaporation solution growth tech-
nique using chloroform as a solvent. After a week, yellow, transpar-
ent, needle-like crystals were obtained. 1H NMR (500 MHz, CDCl3,
300 K): d = 8.17–8.10 (m, 8 H, CHN), 7.48–7.36 (m, 8 H, 6-Ph), 6.99–
6.89 (m, 8 H, 4-Ph), 4.23–4.03 and 3.14–3.00 (m, 2 V 8 H, CH2N), 1.81–
1.74 and 1.52–1.50 (m, 2 V 8 H, -CH2-), 1.40–1.27 (m, 16 V 9 H, tBu),
0.73–0.63 and 0.52–0.39 ppm (m, 2 V 8 H, SiCH2); 13C NMR (126 MHz,
CDCl3): d = 172.8 (C=N), 169.2 (C-O), 141.6 (3-Ph), 135.2 (5-Ph),
129.7 (4-Ph), 129.1 (6-Ph), 116.7 (1-Ph), 63.1 (CH2N), 35.7 (CMe3),
33.9 (CMe3), 31.6 (-(CH3)3), 29.6 (-(CH3)3), 24.6 (CH2), 8.4 ppm (SiCH2);
29
Si{1H} CP MAS NMR (59.6 MHz): d = @66.8 (s); DRIFT: ṽ = 2952 (s,
nC-H), 2904 (m, nC-H), 2866 (m, nC-H), 1613 (s, nC=N), 1531 (m), 1434 (m,
dC-O), 1254 (s, nC-O), 1097 (s, nSi-O-Si), 539 (w, nZn-O), 517 cm@1 (w, nZn-N);
HRMS (ESI + , FT), m/z: 1433.5799 [M+ +2 H]2 + (calcd 1433.5784); ele-
mental analysis calcd (%) for C144H216N8O20Si8Zn4 (2865.50): C 60.36,
H 7.60, N 3.91, Zn 9.13; found: C 60.48, H 7.54, N 3.86, Zn 9.258;
Chem. Eur. J. 2020, 26, 13686 – 13697 www.chemeurj.org 13695
UV/Vis (dichloromethane, 293 K) l (log e): 232 (6.21), 248 (6.20), 279
(5.96), 383 nm (5.73 m@1 cm@1); decomposition onset temperature
(DTG, 10 8C min@1): 334 8C (air), 346 8C (N2); temperature of decom-
position to Zn2SiO4 (determined by TGA measurement, air,
10 8C min@1), residue yield: 520 8C, 24.52 % (calcd 25.85 %).
Zn4@POSS-1: Method B. Under nitrogen, ZnEt2 (0.77 mL,
0.7657 mmol, 4.0 equiv) was added dropwise to a solution of
POSS-1 (0.500 g, 0.1914 mmol) in toluene (50 mL) at @78 8C. The
reaction mixture was stirred overnight at ambient temperature.
After that, the solvent was evaporated. The resulting yellow solid
was recrystallized from chloroform at @15 8C to yield 84 % (0.461 g,
0.161 mmol) Zn4@POSS-1.
Coupling reaction of epoxide and CO2
General procedure: A 20 mL Pyrex vial was charged with epoxide
(4.4 mmol), Zn4@POSS-1 (1 mol %), and co-catalyst (4 mol %,
1 equiv rel. to Zn) and filled with CO2. The vial was then closed.
The mixture was stirred at a constant temperature during the time
of the reaction. The vial was then cooled in an ice bath. The con-
version of epoxide to cyclic carbonate was confirmed through
analysis of the post-reaction mixture by means of 1H NMR spectros-
copy, using mesitylene as an internal standard. To determine isolat-
ed yields, following the reaction the mixture was purified by
means of flash chromatography (n-hexane/EtOAc (3:1) for en-
tries 1–3, 5, and 6, hexane/EtOAc (1:1) for entries 4 and 7). Cyclic
carbonates were characterized in accordance with literature
data.[92, 93]
Yield–time plot of the reaction: A J. Young NMR tube was
charged with epoxide (0.22 mmol), Zn4@POSS-1 (1 mol %), co-cata-
lyst (4 mol %, 1 equiv rel. to Zn) and [D7]DMF (0.6 mL) and then it
was purged with CO2. The reaction was heated in an oil bath at a
constant temperature. The 1H NMR spectrum of the reaction was
collected at regular time intervals using a 10 s relaxation delay. Re-
action plots were generated by integrating the resonances of the
reactants and products for each time measurement, with the inte-
grations normalized to mesitylene as an internal standard present
in the reaction. The average of two resonances for each species
was used to determine the molar concentration with an estimated
error of less than 5 %.
The TOF of epoxide conversion was estimated by using the data
obtained at epoxide conversions of less than 10 %.
Recycling experiments: For catalyst recycling experiments,
Zn4@POSS-1 was recycled by filtration, washing with hexane, and
then it was dried under vacuum. The recycled catalyst was then
reused for the next run without further purification. In each subse-
quent run, a fresh portion of TBAI was added.
Acknowledgments
The authors acknowledge the National Science Centre, Poland
UMO-2016/21/N/ST5/03293 (M.J.) and National Centre for Re-
search and Development (Grant TANGO1/266660/NCBR/2015)
(S.S.) for support of this research. M.J. gratefully acknowledges
financial support by the Foundation for Polish Science (FNP)
via the START stipend program.
Conflict of interest
The authors declare no conflict of interest.
T 2020 Wiley-VCH GmbH
 Full Paper
Chemistry—A European Journal doi.org/10.1002/chem.202002996
Keywords: carbon dioxide · cyclic carbonates · epoxides ·
polyhedral silsesquioxanes · zinc complexes
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Manuscript received: June 22, 2020
Revised manuscript received: July 22, 2020
Accepted manuscript online: July 24, 2020
Version of record online: September 24, 2020
T 2020 Wiley-VCH GmbH