BTP - Sem. 7: Topic-Iron Catalyzed CO2 Hydrogenation To Formate Enhanced by Lewis Acid Co-Catalysts

BTP – Sem.
7th
Topic-Iron catalyzed CO2 hydrogenation to

formate enhanced by Lewis acid co-
catalysts.
By-Kumar Snehit
130122025
Chemical Science and Technology
Superviser: Dr. Akshai Kumar A S
ABSTRACT
1. A family of iron(II) carbonyl hydride complexes supported
by either a bifunctional NNN ligand containing a secondary
amine. NNN ligand with a tertiary amine prevents metal–
ligand cooperativity, was found to promote the catalytic
hydrogenation of CO2 to formate in the presence of
Bronsted base.
2. For the secondary amine supported system, turnover
numbers of approximately 9000 for formate production
were achieved, while for catalysts supported by the
tertiary amine ligand, nearly60 000 turnovers were
observed.
3. The Lewis Acid co-catalysts raise the turnover number by
more than an order of magnitude in each case. In the
secondary amine system, studies show that the Lewis Acid
in disrupting an intramolecular hydrogen bond between
the NNN ligand N–H moiety and the carbonyl oxygen of a
formate ligand in the catalytic resting state.
4. This destabilization of the iron-bound formate accelerates
product extrusion, the rate-limiting step in catalysis. In
systems supported by ligands with the tertiary amine, it
was found that the Lewis Acid enhancement originates
from cation assisted substitution of formate for
dihydrogen during the slow step in catalysis.
INTRODUCTION
1.The increasing volatility in price and the negative
environmental impact associated with fossil fuel utilization for
energy and commodity chemical production continues to spur
basic research into the exploitation of renewable carbon
resources.
2. CO2 is an attractive target for transitioning the chemical
industry to sustainable feedstocks, due to its incredible
abundance, cheap availability and low toxicity.
3. Formic acid is an especially interesting CO2 reduction
product given its use in numerous agrochemicals and
preservatives,3 as well as its potential role as a material for
chemical hydrogen storage (CHS) in renewable energy
applications.
4. Then high value of TON and TOF of the above case often
demonstrate the remarkable potential for catalytic CO2
hydrogenation to formate, but also motivate the development
of earth abundant catalytic systems, which are expected to
enhance the sustainability and economic feasibility of this
transformation.
5.Around 1976, CO2 hydrogenation to formate containing first

row transition metal were described. TONs were low. As a
result for many decades significantly more attention was
devoted to the study of heterogeneous catalysts containing
first-row transition metals.
6.However due to discovery of Fe and Co catalyst have lead to

more efficient homogenous catalyst. For example, Fujita et al.
reported a Cp*Co (Cp* ¼ h5-C5Me5) complex supported by a
dihydroxy-bipyridine ligand that is capable of 59 turnovers to
formate in aqueous bicarbonate,14 while Linehan and
coworkers described an even more impressive TON of 9400
using (Me2PCH2CH2PMe2)2CoH.
7. Collectively these discoveries establish that earth abundant

metals are capable of promoting CO2 hydrogenation, but their
activities lag far beyond those of precious metal catalysts.It has
been recently found that the activity of Fe catalyst was much
better than other catalysts for the dehydrogenation of formate.
8. The impressive activity is dependent on the presence of a

Lewis acid co-catalyst, such as LiBF4, which preliminary
mechanistic studies indicate aids in the decarboxylation of an
iron-formate intermediate.
9.Here we report the hydrogenation of CO2 in the presence of

Fe based on NNN ligand catalyst. The TON is about 60000 far
graeter than any other catalyst. It is due to presence of Lewis
Acid co-catalyst.
THEORY
The net reaction is given above has catalyst and co catalyst.

1.
COMPUTATIONAL SECTION
1.DFT calculations were performed to provide further insight
into the mechanism of CO2 hydrogenation using Fe catalyst.
We employed smaller model Fe complexes in the calculations
by keeping the isopropyl groups of the nitrogen ligands. It has
previously been demonstrated that this change has only a
minor effect on the energetics of NNN supported Fe complexes.
2. The relative free energies reported below were obtained at

the B3LYP/Lan L2DZ level of DFT and relate to standard
conditions . At 298 K and 1bar.
3.Then we run the values obtained from above in the putty

shell to obtain the free energies of the compounds.
4. In our computational study we explore pathways for full

hydrogenation of CO2 along the four-step reaction sequence
depicted in Scheme given below. Accordingly, we discriminate
between three individual reaction sequences in the following
discussion of the computational results: (A) Attaching H2 on the
catalyst.CO2 reacts on the resultant one (B) Transition State 2.
(C) Transition State 3 to the catalyst and formate.
TS1
H2 + ->RXN1
A B
CO2 +
TS2 ->RXN2
B
C
TS3
+ HCOOH ->RXN3
TS1:
E =N (iPr)2
TS2:
TS3:
RESULTS
It is now known that the hydrogenation of CO2 in the presence
of Fe catalyst happens in the following pathway.
1. Firstly H2 gas reacts with catalyst to form the hydrolysed

product via formation of a transition state(TS1) as shown
in the reaction 1.In TS1 we see that each hydrogen of H2
interacts with Fe and N of the catalyst forming a tetragonal
ring structure.
2. Then CO2 is made to react with the product of Rxn1 in

order to form a Transition State(TS2).In the TS2 we see
that Oxygen of CO2 interacts with Fe and hydrogen of Fe
interacts with carbon of CO2 forming a tetra gonal
structure.
3. The transition state 2 rearranges in such a way that the

hydrogen of Fe removes itself from Fe and attaches itself
to the oxygen of OCO group while OCO forms a bond with
Fe atom.
4. Then transition State 3 forms when the product of rxn2

rearranges in such a manner that the hydrogen of nitrogen
group of catalyst forms H-bonding with the COHO group in
the catalyst leading to the formation of 6 membered ring.
5. The ring rearranges and our initial catalyst with formic acid
is formed.
The free energy graph for the reaction compounds.
Stationary points identified along the individual routes are

denoted correspondingly by preceding capital letters.
1. In the graph we can see that from A to B there is slight

decrease in the free energy.By this we can conclude that
the compound B is more thermodynamically stable than A
since delta G is negative.
2. Similarly we can see that form B to C the reaction is more
easier since difference in the free energies of both is highly
negative leading to more stable product C. awe can also
say that reaction from compound B to compound C is
exothermic since there is not much of a change in the
entropy of the system.
3. From C to D we can see that the difference in free energy
is still negative but the value has lessened from the
previous case.But still it shows that the compound D is
relatively stable than the compound C.
CONCLUSION
We have demonstrated that a family of NNN-supported Fe
complexes generates highly active catalysts for the
hydrogenation of CO2. In the absence of water, these catalysts
rapidly convert CO2 to methyl formate and H2O.
In both cases dramatic improvements in TON and TOF were

observed when LA co-catalysts were present.
The tertiary amine supported complex (iPr2NMeN)Fe(H)

CO, achieved approximately 60 000 turnovers, more than
any order of magnitude greater than other iron catalysts and
far superior to any earth abundant metal catalysts reported to
date.
(RNNMeP)Fe(H)CO was activated by base to produce a

(RNNMeP)Fe(H)2CO species which rapidly inserts CO2. The
resulting formate complex, (iPr2NNMeN) Fe(H)CO(HCO2), was
identifed as the catalytic resting state.
In this case the lewis acid assisted in formation of formate for

dihydrogen substitution which yields a transient cationic
iron(II) dihydrogen complex.
As we see how the most earth abundant metal catalysts are

made to operate via similar mechanisms for CO2 hydrogenation
it is possible that the use of lewis acid co-catalyst will help in
further increase in the performance of CO2 reduction.
Such improvements in CO2 hydrogenation at iron may

help related catalyst systems to form products such as
methanol.
These methods are important for the storage of CO2 which is a

greenhouse gas and thus will help in lessening of the global
warming effect .

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BTP – Sem.

Topic-Iron catalyzed CO2 hydrogenation to

5.Around 1976, CO2 hydrogenation to formate containing first

6.However due to discovery of Fe and Co catalyst have lead to

7. Collectively these discoveries establish that earth abundant

8. The impressive activity is dependent on the presence of a

9.Here we report the hydrogenation of CO2 in the presence of

The net reaction is given above has catalyst and co catalyst.

2. The relative free energies reported below were obtained at

3.Then we run the values obtained from above in the putty

4. In our computational study we explore pathways for full

1. Firstly H2 gas reacts with catalyst to form the hydrolysed

2. Then CO2 is made to react with the product of Rxn1 in

3. The transition state 2 rearranges in such a way that the

4. Then transition State 3 forms when the product of rxn2

Stationary points identified along the individual routes are

1. In the graph we can see that from A to B there is slight

In both cases dramatic improvements in TON and TOF were

The tertiary amine supported complex (iPr2NMeN)Fe(H)

(RNNMeP)Fe(H)CO was activated by base to produce a

In this case the lewis acid assisted in formation of formate for

As we see how the most earth abundant metal catalysts are

Such improvements in CO2 hydrogenation at iron may

These methods are important for the storage of CO2 which is a

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