[OSSO]-Type Fe(III) Metallate as Single-Component Catalyst for the CO2 Cycloaddition to Epoxides

Article abstract of DOI:10.1002/adsc.201801240

A new [OSSO]-Fe(III) metallate complex was prepared and characterized. We demonstrated that such metallate is the real catalytic active species for the cycloaddition of CO₂ to the epoxides, formed from the in situ reaction of the related [OSSO]-Fe(III) neutral complexes and tetrabutylammonium bromide. The metallate complex was used as a single component catalyst for the formation of cyclic organic carbonates from ten epoxides and CO₂ at 1 bar pressure with good activity. (Figure presented.).

Full text of DOI:10.1002/adsc.201801240

Title: [OSSO]-Type Fe(III) Metallate as Single-Component Catalyst for
the CO2 Cycloaddition to Epoxides
Authors: Francesco Della Monica, Antonio Buonerba, Veronica
Paradiso, Stefano Milione, Alfonso Grassi, and Carmine
Capacchione
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10.1002/adsc.201801240
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
[OSSO]-Type Fe(III) Metallate as Single-Component Catalyst
for the CO2 Cycloaddition to Epoxides
Francesco Della Monica,a Antonio Buonerba,a Veronica Paradiso,a Stefano Milione,a
Alfonso Grassi,a and Carmine Capacchionea,*
a
Dipartimento di Chimica e Biologia “Adolfo Zambelli” Università degli Studi di Salerno, Via Giovanni Paolo II,
84084 Fisciano (SA), Italy.
Fax: (+39)-089-969603; phone: (+39)-089-969543; e-mail: ccapacchione@unisa.it
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
noted that while it is common to denote the Lewis-
prepared and characterized. We demonstrated that such acidic metal as the “catalyst” and the nucleophile as
Abstract. A new [OSSO]-Fe(III) metallate complex was
metallate is the real catalytic active species for the
cycloaddition of CO2 to the epoxides, formed from the in
situ reaction of the related [OSSO]-Fe(III) neutral
complexes and tetrabutylammonium bromide. The
metallate complex was used as a single component catalyst
for the formation of cyclic organic carbonates from ten
epoxides and CO2 at 1 bar pressure with good activity.
the “cocatalyst”, the latter promotes the cycloaddition
reaction even in the absence of the metal complex,
albeit with lower activity.[6] On the contrary, only few
metal complexes give good conversion of the
epoxides to the cyclic carbonates without the addition
of an excess of the suited nucleophile.[7] These cases
are usually based on dinuclear metal complexes, or a
bimetallic reaction mechanism is invoked in which
one metal centre furnishes the nucleophile and
another one activates the epoxide. However, a picture
considering a possible interaction of the nucleophile
with the metal centre is usually not taken into account.
Keywords: carbon dioxide fixation; iron; cycloaddition;
homogeneous catalysis
The use of carbon dioxide (CO2) as chemical
feedstock is a growing area of interest for chemists
and chemical engineers, not only because CO2
reutilization can contribute to the reduction of the
carbon footprint in many chemical processes, but also
because it is a cheap, non-toxic molecule that can be
advantageously employed, replacing more toxic C1
sources such as carbon monoxide and phosgene.[1] In
this field, the cycloaddition of CO2 to the epoxides is
one of the most studied reaction,[2] due to the
favourable thermodynamic of the overall process, and
to the usefulness of the target molecules that can be
used as high-boiling polar solvents,[3] in batteries as
ion carriers,[4] and as chemical intermediates.[5]
The catalysts that have shown the best
performances are those based on binary systems,
constituted by a Lewis acid and a nucleophile.[2g-k] In
the widely accepted mechanistic scenario (Scheme 1)
the role of the metal centre is to activate the epoxide
(a) for the nucleophilic attack of the anion (b), giving
the formation of the metal-alkoxo intermediate that
undergoes the CO2 insertion (c), followed by the
back-biting (d) with formation of the cyclic carbonate.
Usually, the most common nucleophiles used in the
binary systems are those based on quaternary
ammonium or phosphonium salts, or ionic liquids
bearing nucleophilic counter anions.[2] It should be
Scheme 1. General mechanism for the cycloaddition of
CO2 to the epoxides.
Lately, we reported the use of a new class of
[OSSO]-type Fe(III) complexes, activated by
tetrabutylammonium bromide (TBAB), for the
synthesis of cyclic organic carbonates (COCs) under
very mild reaction conditions.[8] We demonstrated that,
despite the mononuclear nature of these complexes,
the reaction mechanism proceeds through a bimetallic
1
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10.1002/adsc.201801240
Advanced Synthesis & Catalysis
pathway and, supported by UV-vis measurements and
Since the presence of an equilibrium between
DFT calculations, we proposed that the Fe-complexes chloride and bromide cannot be excluded a priori, the
react with the cocatalyst, leading to the formation of a complex 4 was prepared starting from the bromide
metallate species which is the real catalytic active complex 2, in order to avoid the presence of chloride
species (Scheme 2).
anion in the reaction medium. The complex 4 was
fully characterized by elemental analysis, NMR
Evans method, high resolution MS, UV-vis and FT-
IR spectroscopy and all the analysis confirmed the
formation of the desired di-bromide substituted
metallate species (see Supporting Information). The
same analyses conducted on the complex 3 support
the formation of a similar species, but some
differences can be detected. For example, the FT-IR
spectra of 3 and 4 are almost superimposable, except
for some bands around 800 and 1050 cm-1 (Figure 1).
Scheme 2. Proposed in situ formation of [OSSO]-Fe(III)
metallate complexes.
Here we report on the synthesis, isolation and
characterization of this metallate species, and its use
as single component catalyst for the synthesis of
COCs from CO2 and epoxides. The putative real
catalyst was prepared independently from the
previously studied chloride complex 1 and the new
bromide complex 2 (Scheme 3). The complex 2 was
prepared with the same procedure used for the
complex 1,[8] and fully characterized (see Supporting
Information). At first, the reaction of 1 with 2
equivalents of TBAB was performed in
dichloromethane (DCM). Under these conditions, the
release of tetrabutylammonium chloride (TBAC)
occurs, so the complex 3 was recovered by extraction
with a toluene/hexane mixture to obtain the pure
product.
Figure 1. Comparison of the FT-IR spectra of the complex
3 (red line) and the complex 4 (blue line).
Such differences can be ascribed to the incomplete
substitution of chloride with bromide in the complex
3, with the formation of a mixed chloride/bromide
species. The ESI FT-ICR MS analysis revealed the
different composition of the complexes 3 and 4
(Figures S14 and S15). For comparison, the in situ
formation of the metallate species was confirmed by
the mass spectra of the complexes 1 and 2,
respectively in the presence of 2 and 1 equivalents of
TBAB (Figure S12 and S13).
To elucidate the role of the halide in the
cycloaddition reaction, the complexes 1-2 were tested
under the same reaction conditions, varying the
TBAB/Fe molar ratio from 0/1 to 5/1. The reaction of
CO2 with hexene oxide (5a) was selected as
benchmark, and the results are listed in Table 1. Both
the complexes 1 and 2 were found to be inactive in
the absence of TBAB (entries 1 and 6, Table 1). The
presence of 0.5 equivalents of TBAB activates the
catalysts, obtaining comparable conversions in both
cases (entries 2 and 7, Table 1). Increasing the TBAB
loading to 1 or 2 equivalents with respect to the
Fe(III) concentration, the complex 2 showed higher
activity (entries 3-4 and 8-9, Table 1), reaching a
conversion of 84 % with a TOF of 35 h-1. Using an
excess of TBAB, both the systems reached a
conversion around 90 % (entries 5 and 10, Table 1).
Scheme 3. Synthesis of [OSSO]-Fe(III) complexes 1-4.
2
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10.1002/adsc.201801240
Advanced Synthesis & Catalysis
Table 1. 5a/CO2 coupling promoted by 1-4.
with very close values of TOF (entries 12 and 15,
Table 1).
To compare the activities of 3 and 4 with those of 1
and 2, the reaction was repeated in the presence of 3
equivalents of TBAB with respect to the metallate
(entries 13 and 16, Table 1). The presence of TBAB
has a beneficial role on the reaction, reaching a TOF
of 38.5 h-1 in the case of 4, that is the same TOF
obtained with the complex 2 in the presence of an
excess of TBAB (entry 10, Table 1). The benign
effect of TBAB on the catalytic activity can be
explained taking into account that, after the
dissolution of the catalyst in the neat epoxide, an
equilibrium between the free metallate and the
complex binding the substrate takes place (Scheme 4).
Entry Complexa) TBAB TBAB/Fe Convb) TOFc)
mol%
mol% mol/mol
mol% h-1
1
2
3
4
5
6
7
8
1 (0.1)
1 (0.1)
1 (0.1)
1 (0.1)
1 (0.1)
2 (0.1)
2 (0.1)
2 (0.1)
2 (0.1)
2 (0.1)
1 (0.05) +
3 (0.05)
3 (0.1)
3 (0.1)
2 (0.05) +
4 (0.05)
4 (0.1)
4 (0.1)
-
0/1
0.5/1
1/1
2/1
5/1
0/1
0.5/1
1/1
2/1
5/1
-
0
-
0.05
0.1
0.2
0.5
-
0.05
0.1
0.2
0.5
-
11
32
58
89
0
10
53
84
92
16
4.5
13.5
24
37.0
-
4.0
22
35
38.5
6.5
9
10
11d)
12d)
13d)
14e)
-
0.3
-
-
3/1
-
59
86
24
24.5
36
10
Scheme 4. Equilibrium involving the coordination of 5a to
the Fe centre of the metallate 4.
15e)
16e)
-
0.3
-
3/1
61
92
25.5
38.5
a)Reaction conditions: 5a = 4.15 × 10−2 mol; T = 35 °C;
P(CO2) = 1 bar; reaction time = 24 h, neat. b)Determined by
1H NMR using mesitylene as internal standard. The
Since the ring opening of the Fe-coordinated
epoxide involves the Fe-mediated attack of a bromide
anion, the presence of an excess of TBAB moves the
equilibrium to the left, granting the proper amount of
the metallate in the reaction medium.
selectivity toward the formation of 6a was always found to
−1
be >99%. c)Turnover frequency (mol5a · molCatalyst
·
reaction time−1). d)Complex 3 obtained from complex 1.
e)Complex 4 obtained from complex 2.
The complex 4 was then tested as single
component catalyst for the conversion of a group of
variously substituted epoxides in the corresponding
COCs, using a catalyst loading of 0.2 mol% in order
to shorten the reaction time to 6 hours (Scheme 5).
The reaction of the benchmark substrate 5a proceeds
well, with a TOF of 40 h-1. The less encumbered
epoxide 5b reacts faster, with an initial TOF of 54 h−1.
Increasing the length of the alkyl chain in the case of
epoxy-dodecane 5c, results in an attenuation of the
catalytic activity, probably because the polarity of the
reaction medium affects the equilibrium showed in
Figure 4. The reaction proceeds slower even in the
case of styrene carbonate 5d, this difference in
reactivity can be reasonably ascribed to electronic
effect of the phenyl ring.[9]
Compared to 5a, the reactions of the glycidyl
epoxides 5e-g proceed faster, with a TOF as high as
57 h-1 in the case of methyl glycidyl ether. In the case
of epichlorohydrin 5h and disubstituted substrates 5i-j
a catalyst loading of 0.4 mol% was used, since the
reaction of these epoxides was found to proceed
slower under the mild reaction conditions used for the
study,[8] and the formation of the corresponding
carbonates 6h-j was accomplished with good
activities. In particular, 6i and 6j were obtained with a
high degree of stereoretention with respect to the
starting epoxide.
Since the ring opening of the epoxide was
identified as the rate determining step of the reaction
promoted by the system 1/TBAB,[8] the higher
activity of the system 2/TBAB can be ascribed to the
higher nucleophilicity of the bromide with respect to
the chloride. Indeed, since TBAC is formed by the
reaction of 1 with TBAB, and the free chloride anion
participates in the equilibrium between the neutral
and anionic form of the complex, and excess of 5
equivalents of TBAB is required to obtain catalytic
activity similar to that of complex 2 with only 2
equivalents of TBAB (compare entries 5 and 9, Table
1).
In order to confirm that the metallate complex is
the real catalytic active species, the complexes 3 and
4 were then used in the same reaction (entries 11-16,
Table 1). At first, two 1/1 mixtures of 3 or 4 with 1 or
2 respectively, were tested leaving the Fe total
loading to 0.1 mol% (entries 11 and 14, Table 1).
With our delight both the mixtures were active,
leading to the selective formation of the hexene
carbonate 6a. The mixture of 2 and 4 was the most
active, confirming that the presence of chloride slows
down the progress of the reaction. When used alone,
the two complexes gave almost the same conversion,
3
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10.1002/adsc.201801240
Advanced Synthesis & Catalysis
Experiemental Section
General considerations. All manipulation involving air-
and/or moisture-sensitive compounds were performed
under nitrogen atmosphere using standard Schlenk
technique and a MBraun glovebox. Toluene (99.5%;
Sigma-Aldrich), THF (99%; Sigma-Aldrich) and DCM
(99.9%, Sigma-Aldrich) were used as received or refluxed
for 48 h over sodium, sodium ketyls or LiAlH4 and distilled
before use for moisture- and oxygen-sensitive reactions.
All other reagents were used as received (TCI or Sigma-
Aldrich) or distilled under reduced pressure over calcium
hydride. Deuterated solvents were purchased from Euriso-
Top or Sigma-Aldrich and used as received. NMR spectra
were collected on Bruker Avance spectrometers (400, 300
or 250 MHz for 1H): the chemical shifts were referenced to
tetramethylsilane (TMS) as external reference using the
residual protio signal of the deuterated solvents. The ligand
L and the complex 1 were prepared as reported in reference
8. Measurements of effective magnetic moments were
performed on a Bruker Avance 400 MHz spectrometer in
toluene-d8 using a 5 mm Wilmad coaxial insert NMR tube.
The effective magnetic moment (μeff) was calculated from
μeff = 8χgMwT, where χg (cm3 g−1) is the corrected molar
susceptibility derived from χg = 3Δf/4πfoCMw + χo. Δf is
the shift in frequency (Hz) of the residual protio signal of
the solvent in the presence of the complex from the value
of the pure solvent, C and Mw are respectively the
concentration (mol cm−3) and the molecular weight of the
complex (g mol−1), f0 is the operating frequency of the
spectrometer (Hz), and χ0 is the mass susceptibility of the
pure solvent (−0.6179 × 10−6 cm3 g−1 for toluene-d8). 4π/3
is the shape factor for a cylindrical sample in a
superconducting magnet. Elemental analysis was
performed on a CHNS Thermo Scientific Flash EA 1112
equipped with a thermal conductivity detector. High
resolution Electrospray Ionization Fourier Transform Ion
Cyclotron Resonance Mass Spectrometry (ESI FT-ICR
MS) measurements of complexes were performed on a
Bruker Solaris XR instrument. FT-IR measurements were
carried out on a Bruker Vertex 70 spectrometer equipped
with DTGS detector and a Ge/KBr beam splitter. The
samples were analyzed in the solid state as KBr disks. UV-
Vis spectra were collected on a PerkinElmer Lambda EZ
201 spectrophotometer.
Synthesis of the iron(III) complex 2. Pro-ligand L (2.000
g; 3.59 mmol) was dissolved in THF (100 mL). The
solution was added to a suspension of sodium hydride
(0.190 g; 7.92 mmol) in THF (45 mL) and the mixture
stirred at room temperature overnight. The resulting
suspension was filtered through celite and slowly added at
room temperature to 1.0525 g of anhydrous iron(III)
bromide (3.56 mmol) dissolved in 100 mL of THF. The
rapid change of the color to the deep purple was observed
and the reaction kept overnight. The mixture was then
filtered through celite and the solvent removed under
reduced pressure affording a deep purple crystalline solid.
Yield: 2.58 g, 95.1 %. Elemental analysis calcd. for
C38H58BrFeO3S2: C, 59.84; H, 7.66; S, 8.41; found: C,
59.79; H, 7.72; S, 8.49. µeff = 5.66 µB at 30 °C.
Scheme 5. Scope in epoxides. Reaction conditions:
Epoxide = 4.15 ∙ 10−2 mol; 4 = 0.2 mol% T = 35 °C;
P(CO2) = 1 bar; reaction time = 6 h, neat. Conversion
determined by 1H NMR using mesitylene as internal
standard. The selectivity toward the formation of cyclic
carbonate was always found to be >99%. Turnover
−1
frequency = molepoxide · mol4 · reaction time−1). a) 4 = 0.4
mol%. b) 4 = 0.4 mol%; T = 50 °C; P(CO2) = 10 bar;
reaction time = 24 h
Synthesis of the iron(III) complex 3. Complex 1 (0.200 g;
0.28 mmol) and TBAB (0.180 g; 0.56 mmol) were
dissolved in DCM (25 mL). The solution was stirred at
room temperature overnight and the solvent was removed
under reduced pressure. The residue was redissolved in a
toluene/hexane mixture (40 mL, 1/1 vol/vol), filtered
through celite and the solvent removed under reduced
pressure, affording a deep purple powder. Yield: 0.21 g,
78 %. Elemental analysis calcd. for C50H86ClBrFeNO3S2: C,
62.00; H, 8.95; N,1.45; S, 6.62; found: C, 61.64; H, 8.85; N,
1.52; S, 6.58. µeff = 5.96 µB at 30 °C.
In conclusion, we isolated and characterized a new
metallate [OSSO]-Fe(III) complex. This species was
used as single component catalyst for the reaction of
several epoxides under very mild reaction conditions
(Fe = 0.2 mol%; 1 bar of CO2 pressure, 35 °C). Apart
to the good catalytic activity and selectivity of this
system, the results described in this study shed more
light on the role of the onium salts in the metal-
mediated cycloaddition of CO2 to the epoxides. We
believe that these findings are crucial for a better
understanding of the reaction mechanism, and can
serve for the development of new high active catalysts.
Synthesis of the iron(III) complex 4. Complex 2 (1.500 g;
1.97 mmol) and TBAB (0.6348 g; 1.97 mmol) were
dissolved in DCM (150 mL). The solution was stirred at
room temperature overnight and the solvent was removed
4
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10.1002/adsc.201801240
Advanced Synthesis & Catalysis
under reduced pressure, affording a deep purple powder.
Yield: 1.5519 g, 77.8 %. Elemental analysis calcd. for
C50H86Br2FeNO2S2: C, 59.28; H, 8.56; N, 1.38; S, 6.33;
found: C, 59.34 H, 8.60; N, 1.50; S, 6.38. µeff = 5.76 µB at
30 °C.
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Typical procedure for CO2/5a coupling (referred to
entry 16, Table 1). A 60 mL stainless steel pressure
reactor equipped with a magnetic stirring bar was charged,
under CO2 atmosphere, with 42.0 mg of catalyst 4 (4.15 ∙
10−5 mol) and 40.1 mg of TBAB (1.25 ∙ 10−4 mol)
dissolved in 5.0 mL of 5a (4.15 ∙ 10−2 mol). The reaction
mixture was pressurized with CO2 at 1 bar and stirred at
35 °C for 24 h. The reactor was cooled with ice, the CO2
released, 0.58 mL of mesitylene (4.15 ∙ 10−3 mol) was
added as an internal standard and the mixture was analyzed
1
by H NMR spectroscopy using CDCl3 as solvent (Figure
S23). Conversion = 92.0 %.
Typical procedure for CO2/epoxide coupling promoted
by 4 (referred to Scheme 5). A 60 mL stainless steel
pressure reactor equipped with a magnetic stirring bar was
charged, under CO2 atmosphere, with 84.0 mg of catalyst 4
(8.3 ∙ 10−5 mol) dissolved in 5.0 mL of 5a (4.15 ∙ 10−2 mol).
The reaction mixture was pressurized with CO2 at 1 bar and
stirred at 35 °C for 6 h. The reactor was cooled with ice,
the CO2 released, 0.58 mL of mesitylene (4.15 ∙ 10−3 mol)
was added as an internal standard and the mixture was
analyzed by 1H NMR spectroscopy using CDCl3 as solvent
(Figure S24). Conversion = 48.0 %.
[3]a) B. Schaffner, F. Schaffner, S. P. Verevkin, A. Borner,
Chem. Rev. 2010, 110, 4554-4581; b) M. Sathish, K. J.
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Arav, M. North, Green Chem. 2017, 19, 1685-1691.
Only for propylene carbonate 6b, the isolated yield was
determined because of the volatile nature of the epoxide
5b: the volatiles were removed under vacuum, the sample
treated with pentane to precipitate the catalyst, filtered over
silica and the solvent removed by rotary evaporation; yield
= 2.75 g (65%).
[4] a) X. L. Wei, W. Xu, M. Vijayakumar, L. Cosimbescu,
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Acknowledgements
Ministero dell’Istruzione dell’Universitꢀ e della Ricerca (MIUR,
Roma, Italy) and Universitꢀ degli Studi di Salerno (FARB 2016-
ORSA165551) are acknowledged for funding. The authors
acknowledge Dr. Patrizia Oliva, Dr. Patrizia Iannece, Dr.
Mariagrazia Napoli, and Dr. Ivano Immediata from University of
Salerno for technical assistance.
[6] a) V. Caló, A. Nacci, A. Monopoli, A. Fanizzi, Org.
Lett. 2002, 4, 2561-2563; b) F. Della Monica, A.
Buonerba, A. Grassi, C. Capacchione, S. Milione,
ChemSusChem 2016, 9, 3457-3464.
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10.1002/adsc.201801240
Advanced Synthesis & Catalysis
COMMUNICATION
[OSSO]-Type Fe(III) Metallate as Single-
Component Catalyst for the CO2 Cycloaddition to
Epoxides
Adv. Synth. Catal. Year, Volume, Page – Page
Francesco Della Monica, Antonio Buonerba,
Stefano Milione, Alfonso Grassi, Carmine
Capacchione*
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