A MOF-assisted phosphine free bifunctional iron complex for the hydrogenation of carbon dioxide, sodium bicarbonate and carbonate to formate

Article abstract of DOI:10.1039/c8cc09771b

The hydrogenation of carbon dioxide into formic acid (FA) with Earth-abundant metals is a vibrant research area because FA is an attractive molecule for hydrogen storage. We report a cyclopentadienyl iron tricarbonyl complex that provides up to 3000 turnover number for carbon dioxide hydrogenation when combined with a catalytic amount of the chromium dicarboxylate MOF MIL-53(Cr). To date, this is the highest turnover number reported in the presence of a phosphine-free iron complex.

Full text of DOI:10.1039/c8cc09771b

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DOI: 10.1039/C8CC09771B
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MOF-Assisted Phosphine Free Bifunctional Iron Complex for the
Hydrogenation of Carbon Dioxide, Sodium Bicarbonate and
Carbonate to Formate.
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
b
c
b
Sébastien Coufourier, Sylvain Gaillard, Guillaume Clet, Christian Serre, Marco Daturi, * Jean-
a
DOI: 10.1039/x0xx00000x
Luc Renaud *
www.rsc.org/
Abstract: Hydrogenation of carbon dioxide into formic acid (FA) Gonsalvi12 disclosed recently well-defined iron hydride
with Earth-abundant metals is a vibrant research area, because FA complexes for the reduction of carbon dioxide into formates or
is an attractive molecule for hydrogen storage. We report a formamides. Bernskoetter and Hazari have described the most
cyclopentadienyl iron tricarbonyl complex that provides up to 3000 impressive results with a Turnover number (TON) of up to
turnover numbers for carbon dioxide hydrogenation when 60000 over 24h with a [Fe(H)(BH
4
)(PNP)(CO)] complex and in
combined with a catalytic amount of the chromium dicarboxylate the presence of DBU and LiOTf, with a 7.5 : 1 loading ratio, in
1
3
MOF MIL-53(Cr). To date, this is the highest turnover number THF at 80 °C. However, replacing noble metals by inexpensive,
reported in the presence of a phosphine free iron complex.
more abundant and biocompatible iron complexes to perform
hydrogenation is not the unique criterion for industrial
applications. Even if these complexes paved the way to new
reactivities in iron chemistry, they contain electron-rich, air- and
moisture sensitive and expensive phosphorous ligands. In our
ongoing work on reduction and alkylation using phosphine free
iron complexes, we have synthesized an iron tricarbonyl
complex bearing an electron rich cyclopentadienone ligand
Fossil fuels represent a large part of the global energy. Due to
the depletion of these fossil resources and in the context of
global warming, it is crucial to develop alternative processes.
Hydrogen gas is a potential clean energy vector to replace fossil
fuels, when synthesised via sustainable sources of energy.
However, its storage and its transport remain a problematic
issue. Dehydrogenation of formic acid (4.4 wt. % H
2
) or
(
complex Fe1, Figure 1), which is more active than the well
methanol (12.6 wt. % H ) has been proposed as an alternative
2
14-15
known Knölker's complex (Fe2, Figure 1).
We and others
solution for hydrogen storage. The current synthesis of formic
acid and methanol is based on the use of nonrenewable
have also demonstrated that these complexes could reduce
15a-16
sodium carbonate.
TON up to 1200 were reached with
1
feedstocks. Carbon dioxide is, in sharp contrast, an abundant,
complex Fe1. We considered that our new cyclopentadienone
iron tricarbonyl complex could be an alternative solution for the
hydrogenation of carbon dioxide.
2
non-toxic and inexpensive C1 carbon source. Its hydrogenation
can deliver, in the presence of a catalyst, formic acid and/or
methanol, moreover decreasing the carbon fingerprint of
related processes. Some organometallic complexes, mainly
based on platinum metals, have been already designed and
3
-4
applied to these applications in the last decades. Despite its
great interest on industrial scale and the exciting challenge, due
to the lower electrophilic character of the carbonyl function, the
hydrogenation of carbon dioxide with Earth-abundant metals is
Figure 1. Cyclopentadienone iron tricarbonyl complexes.
5
-13
10
11
still underdeveloped. Laurenczy and Beller, Milstein, and
To initiate this work, a rapid screening of solvents has been
carried out at 80 °C for 20 h under 20 bar of CO
2
and 40 bar of
H
2
in the presence of triethylamine as base (see the ESI). A 1:1
a. Normandie Univ., LCMT, ENSICAEN, UNICAEN, CNRS, 6 boulevard du Maréchal Juin,
mixture of DMSO and water provided the best result with a TON
of 82. Without any base or iron complex, no reaction was
observed (Table 1, entry 1). Several bases were then evaluated
and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU) led to the
highest TON (Table 1, entries 2-6). High concentration (Table 1,
1
4000 Caen, France.
b.
Normandie Univ., ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et
Spectrochimie (LCS), 14000 Caen, France.
Institut des Matériaux Poreux de Paris, UMR 8004 CNRS, Ecole Normale Supérieure,
Ecole Supérieure de Physique et des Chimie Industrielles de Paris, PSL Research
University, 75005 Paris, France
c.
Electronic Supplementary Information (ESI) available: Preparation details,
optimzation conditions, NMR spectra and characterization of MIL-53(Cr). See
DOI: 10.1039/x0xx00000x
3
entries 3 and 7) and addition of Me NO to activate the iron
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Journal Name
complex (Table 1, entries 7-8) enhanced also the overall activity. for the reduction. For instance the microporoVuiesw 1ArDticlepOonrlienes
A temperature threshold was also required to reach a high chromium(III) terephthalate MIL-53(CDr)OI:(1M0.1IL039/sCta8nCdCs0977fo1Br
conversion and, at 80 or 100 °C, full conversion and a TON of Materials from Institut Lavoisier) has been shown to undergo a
5
00 were obtained (Table 1, entries 8-10). Any variation of the contraction of its lozenge shaped pores in the presence of a low
CO /H ratio led to TON depletion (see ESI). To elucidate the CO pressure at room temperature associated with donor
optimum performance, the catalyst loading was lowered to 0.02 acceptor interactions between the OH groups from the 1D
mol % (Table 1, entries 11-15). A turnover of 1466 to formate inorganic chains and CO molecules, while at higher pressure
2
2
2
2
2
0e,
was finally obtained. Finally, in a last trial, DBU, the most the pores fully expand to accommodate more CO
encountered, but expensive, base in reduction of CO , was
2
2
molecules.
g
replaced by an amidine analogue, namely 1,1,3,3- Initially, we used the same reaction conditions as those
tetramethylguanidine (TMG, Table 1, entry 16). Gratifyingly, a reported previously above (Table 1, entries 15-16), but in the
TON of 1772 to formate was obtained. Even if these results are presence of MIL-53(Cr) (0.05 mol %). To our delight, whatever
1
3
moderate compared to the most active iron complex, they are the base (DBU or TMG), the activities were higher (Table 2,
the highest reported so far with an iron complex without any entries 1-2). Again, TMG, as base, gave better results than DBU
air-sensitive pincer ligand or polydentate phosphine ligand.
and TON's up to 3006 were reached. By comparison with the
sole iron-catalyzed reduction of CO , a two-fold higher TON was
2
Table1. Hydrogenation of carbon dioxide.
reached through this cooperative catalysis. Variation of the
catalytic amount of MOF led to lower TONs (Table 2, entry 3).
When a simple chromium salt such as Cr(acetate) was
3
introduced as Lewis acid, a low TON of 99 was obtained,
highlighting the role of the hybrid material in this hydrogenation
and not simply of the Cr presence (Table 2, entry 4). MIL-53(Cr)
Entry
Fe1
mol %)
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.1
Base
-
Temp.
(°C)
80
80
80
80
80
80
80
80
100
60
80
100
80
100
100
100
Yield
(%)a
-
16.3
24
8.4
10.6
3.6
59.3
100
100
34.3
51.9
59.5
27.1
39.4
29.3
34.5
TONb
(
2
alone or the absence of base led to no reduction of CO (Table
c
1
2
-
82
120
42
53
c
2, entries 5-6). All components are therefore required to deliver
the formate in such a high TON. Finally, a decrease of the CO2 /
H2 pressure led to a lower activity and a TON of 86 (Table 2,
entry 7).
Having demonstrated that a combination of a MOF and a
cyclopentadienone iron tricarbonyl complex could enhance the
catalytic activity, we scrutinized the nature of the metal centre
and the organic linker. MIL-53(Fe) and MIL-53(Al) were then
evaluated, but both MOFs led only to moderate activities (Table
NEt
3
c
3
4
5
6
7
8
9
1
1
1
1
1
1
1
DBU
DABCO
TEOA
c
c,d
c
3
NH aq.
18
c,e
c
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
TMG
297
500
500
172
519
595
542
788
1466
1772
c
f
0
1
2
3
4
5
6
f
2
, entries 8-9). These results might be due, not to the nature of
f
0.1
3
+
3+
3+
the metal centre (Cr , Al and Fe are all good Lewis acids),
but to the stability of the MOF. Indeed, compared to MIL-53(Cr),
f
0.05
0.05
0.02
0.02
f
f
Huang et al. showed that the MIL-53(Al) was poorly stable in
basic aqueous medium at 100 °C.22 Regarding the MIL-53(Fe),
f
the lower activity might also be due to its structural
configuration in the reaction conditions. While the pores are
a
b
1
Yield were determined by H-NMR spectroscopy using DMF as internal standard.
c
Mol of sodium formate per mol of catalyst. CO
2
d
(20 bar), H
2
(40 bar), base (2.5
mmol), Fe1 in DMSO/H
Me
Me
2
O 1/1 (5 mL) for 20 hours. TEOA: triethanolamine. e with
(20 bar), H
O 1/1 (5 mL) for 20 hours.
completely opened under high CO pressure with the MIL-
2
f
3
NO (0.2 mol%). CO
2
2
(40 bar), base (5 mmol), Fe1 (x mol %) and 53(Cr), they are partially opened in the MIL-53(Fe). The
3
NO (x mol %) in DMSO/H
2
absorption ability of the latter is then lower under the reaction
conditions and this might explain its lack of activity.
To enhance the reactivity of our catalytic system, we thought to
combine our system with particles of Metal Organic
Frameworks (MOFs). MOFs are a recent class of 3D crystalline
hybrid micro-/mesoporous materials constructed from
inorganic nodes (clusters, chains, layers…) interconnected with
multi-dentate organic linkers (carboxylates, phosphonates,
azolates…).18 Their unprecedented chemical and structural
diversity led so far to the development of numerous
Table2. MOF-assisted iron complex for the hydrogenation of carbon dioxide.a
1
9
applications with these materials. MOFs, for example, are
particularly suitable for carbon dioxide capture and
2
0
21
sequestration , or for photocatalytic CO
Moreover, their Lewis or Brønsted acid sites, provided by the
inorganic building units, might allow the CO activation. So
these materials might assist / cooperate with the iron complex
2
reduction.
2
2
| J. Name., 2012, 00, 1-3
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Entry
Additive
MIL-53(Cr)
MIL-53(Cr)
MIL-53(Cr)
Base
DBU
TMG
DBU
TMG
TMG
-
TMG
TMG
TMG
TMG
TMG
Yield (%)b
TONc
2173
3006
1900
99
N.R.
N.R.
86
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DOI: 10.1039/C8CC09771B
1
2
43.5
60.1
38
d
3
4
Cr(OAc)
3
2
e
5
MIL-53(Cr)
MIL-53(Cr)
MIL-53(Cr)
MIL-53(Fe)
MIL-53(Al)
MIL-100(Cr)
MIL-101(Cr)
N.R.
N.R.
1.7
12
20.5
4.5
6
f
7
8
9
599
1026
224
1
1
0
1
25.3
1265
a
CO
Me
2
(20 bar), H
NO (0.02 mol %) in DMSO/H
2
(40 bar), base (5 mmol), MOF (0.05 mol %), Fe1 (0.02 mol %) and
b
3
1
2
O 1/1 (5 mL) for 20 hours. Yield were determined
c
by H-NMR spectroscopy using DMF as internal standard. Mol of sodium formate
per mol of catalyst. MIL-53(Cr) (0.02 mol %). without Fe1. CO (10 bar), H (20
2 2
d
e
f
Scheme 2. Proposed mechanism.
bar),
In conclusion, we have demonstrated that a simple combination
of our cyclopentadienone iron tricarbonyl complex and the Cr
dicarboxylate MOF MIL-53(Cr) is able to hydrogenate carbon
dioxide in turnover numbers up to 3006. In contrast to
previously reported iron complexes, this is the first example of
a phosphine free iron complex with such a high activity. This
simple combination is competitive with some of the currently
We extended this work to the hydrogenation of sodium
bicarbonate and carbonate. TON of 1246 was achieved with the
iron complex for the reduction of sodium bicarbonate into
formate, while a slight increase to 1525 was obtained in the
presence of both iron complex and MIL-53(Cr) (Scheme 1).
Moreover, in contrast to CO
MOF has a little influence on the activity (Scheme 1). When
Na CO was employed under the same conditions, the
2
hydrogenation, the amount of
5
-11
reported phosphine-based iron complexes. These results are
also 10 fold higher than the indirect method previously
2
3
conversion was much lower with a TON of 26, but higher than
in the sole presence of the iron complex (TON of 17, Scheme 1).
This result represents also the highest TON reached with an
1
6
reported in the presence of Knölker's complex (Fe3),
highlighting the potential of such combination. Because MOFs
can combine a wide range of functionalized organic linkers and
metal centre, they offer a broad variety of acidity character, of
cationic polarization, of pore size, of surfaces. Their physical and
chemical properties can be modulated and adjusted. Further
work will then be dedicated first to extend this work to the
synthesis/use of various functionalized MOFs and their
application in such reduction to draw a structure/activity
relationship. Second, our work will focus into the mechanism
understanding and the activation of other small molecules.
1
1
Earth abundant metal based-complex.
Scheme 1. Hydrogenation of sodium bicarbonate and sodium carbonate.
Based on these results, the following mechanism might be
proposed. After oxidative release of one CO ligand
Conflicts of interest
“There are no conflicts to declare”.
(intermediate I, Scheme 2), coordination and activation of
hydrogen would lead to the hydride intermediate II (Scheme 2).
We gratefully acknowledge financial support from the
"Ministère de la Recherche et des Nouvelles Technologies",
Normandie Université, CNRS, Région Normandie, Ademe
Agency and the LABEX SynOrg (ANR-11-LABX-0029).
In basic conditions, the hydroxyl group on the cyclopentadienyl
1
5b-e
ancillary ligand would be deprotonated leading to III.
MIL-53(Cr) might have two roles in this catalytic reduction. It
might first uptake CO from the gas phase into the solution and
increase the amount of CO in the medium and second activate
the CO via the OH groups from the 1D inorganic chains (Scheme
). After the hydride transfer, the formate would be released as
The
2
2
2
Notes and references
2
a guanidinium formate regenerating the catalytic species I.
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DOI: 10.1039/C8CC09771B
+
Ph
N
O
N
Ph
Fe
CO
CO
OC
MIL-53(Cr)
Iron complex
TONs up to 3000
A catalytic combination of a phosphine-free iron complex and a MOF allowed the
hydrogenation of carbonic derivatives into formate with TON up to 3000.