Catalytic Decomposition of Methyl Formate in the Presence of Transition Metal Complexes, Phosphine Ligands and Water

Article abstract of DOI:10.1134/S0965544119040078

Abstract: The catalytic decomposition of methyl formate into gaseous components in the presence of transition metal complexes, phosphine ligands, and water has been studied. It has been shown that in the presence of monometallic and bimetallic Rh/Ru catal

Full text of DOI:10.1134/S0965544119040078

ISSN 0965-5441, Petroleum Chemistry, 2019, Vol. 59, No. 4, pp. 412–419. © Pleiades Publishing, Ltd., 2019.
Russian Text © D.N. Gorbunov, V.A. Semernina, M.V. Terenina, Yu.S. Kardasheva, A.L. Maksimov, E.A. Karakhanov, 2019, published in Neftekhimiya, 2019, Vol. 59, No. 3,
pp. 289–296.
Catalytic Decomposition of Methyl Formate in the Presence
of Transition Metal Complexes, Phosphine Ligands and Water
D. N. Gorbunova, *, V. A. Semerninaa, M. V. Tereninaa, Yu. S. Kardashevaa,
A. L. Maksimova, b, and E. A. Karakhanova
aFaculty of Chemistry, Moscow State University, Moscow, Russia
bTopchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
*e-mail: suskab_91@mail.ru
Received November 2, 2018; revised December 1, 2018; accepted December 10, 2018
Abstract—The catalytic decomposition of methyl formate into gaseous components in the presence of tran-
sition metal complexes, phosphine ligands, and water has been studied. It has been shown that in the presence
of monometallic and bimetallic Rh/Ru catalysts, methyl formate can be converted to gas mixtures with high
hydrogen content. These mixtures are suitable for use in hydroformylation, hydroaminomethylation, and
hydroformylation–acetalization reactions; therefore, methyl formate may be thought of as being an alterna-
tive source of synthesis gas in oxo processes.
Keywords: methyl formate, synthesis gas, hydroformylation
DOI: 10.1134/S0965544119040078
The attention of researchers is currently attracted transition metal complexes were synthesized as
to the use of alternative sources of synthesis gas, such described in the literature: Rh(acac)(CO)2 [4],
as methyl formate (MF), formaldehyde, and formic
acid, for the implementation of various processes
involving carbon monoxide [1–3]. It is known that the
catalytic decomposition of MF in the presence of
water (a variety of the water-gas shift reaction) leads to
the formation of a gas mixture, the main components
of which are carbon monoxide and hydrogen. Owing
to the availability and relatively low cost of MF, this
material is promising for a more common use as a
feedstock for petroleum chemistry. The use of MF for
the implementation of hydroformylation reactions and
hydroformylation–acetalization and hydroamino-
methylation tandem reactions is based on the possibil-
ity of converting it to carbon monoxide and, under
certain conditions, a mixture of carbon monoxide,
carbon dioxide, and hydrogen (Fig. 1).
Ru3(CO)12, [5], Rh(cod)2BF4 [6], and Co(acac)3 [7].
Gas–liquid chromatography analysis was con-
ducted on an HP-6990 chromatograph equipped with
a flame ionization detector and a 50-m-long capillary
column coated with the SE-30 phase using tempera-
ture programming and helium as the carrier gas.
Infrared spectra of the complexes were recorded on
a Nicolet IR200 FTIR spectrometer in the range of
300–4000 cm–1. The samples were pelletized in potas-
sium bromide (2%).
Gas chromatography analysis was conducted on a
Chrom-5 chromatograph equipped with a thermal
conductivity detector and a 3-m-long packed column
coated with the Porapak-Q phase at a temperature of
25°C using argon as the carrier gas.
The aim of this study is to analyze the composition
of the gas mixture formed during the MF decomposi-
tion as a function of process conditions, namely, the
catalyst composition, the presence of ligands, and the
amount of water in the reaction mixture.
General Procedure for Methyl Formate Decomposition
The decomposition was run in a 7-mL steel auto-
clave in a temperature range of 130–200°C. The auto-
clave was charged with 2.0 mL (32 mmol) of MF and
required amounts of a metal (iron, manganese, nickel,
cobalt, ruthenium, rhodium, palladium) complex, a
donor ligand (PPh3, PCy3, HNEt2, Xanthos,
TPPTS), and water in amounts of 0.0156–0.025,
0.16–0.4, and 1.6–2.8 mmol, respectively. After that,
EXPERIMENTAL
Methyl formate; the phosphine ligands P(Cy)3,
PPh3, P(OPh)3, Xantphos, and TPPTS; and diethyl-
amine HNEt2 and triethylamine NEt3 (Sigma-
Aldrich) were used as received. Solvents were prepared the autoclave was closed and heated to a required tem-
in accordance with standard procedures. The studied perature. Reaction was run with constant stirring for a
412

CATALYTIC DECOMPOSITION OF METHYL FORMATE
413
O
+ ethylene glycol
H+
O
R
[R'CHO]
Rh, Co or Ru
O
R
O
+
T, °C
Hydroformylation–acetalization
Methyl formate
(catalytic decomposition)
CO + H2
R
R
N
N
+
+ dimethylamine
R
Rh, Co or Ru
[R'CHO]
T, °C
Hydroaminomethylation
Tandem reactions
Hydroformylation
Fig. 1. Hydroformylation and tandem reactions based on hydroformylation using MF as an alternative source of synthesis gas.
given time (2 h). After that, the autoclave was cooled
(6)
HCOOH → CO2 + H2.
to room temperature, and the composition of the
The first stage is the MF decarbonylation; it can be
catalyzed by both metal complexes and bases (e.g.,
amines). Hydrogen generation in the system can occur
through the water-gas shift reaction, which is cata-
lyzed, in particular, by ruthenium complexes with
donor phosphine ligands. The presence of hydrogen is
required for the implementation of the above reac-
tions; therefore, it is relevant to study the MF decom-
position under various conditions, particularly in the
presence of reactants and catalysts that are intended to
be used in hydroformylation (primarily, phosphorus
ligands and metal complexes).
resulting gas mixture was determined by gas chroma-
tography. Gases were sampled using a non-return
water valve. The liquid phase was analyzed using an
internal standard (ethanol).
RESULTS AND DISCUSSION
It is known that the following processes can occur
during the thermal decomposition of MF (100–
200°C) [8–10]:
(1)
(2)
(3)
HCOOCH3 → CO2 + CH4,
HCOOCH3 → CO + CH3OH,
HCOOCH3 → CO + 2H2.
In this study, the catalyst system components and
their ratios were varied to determine the MF conver-
sion, the pressure in the reactor, and the hydrogen
content in the resulting gas mixture.
Decomposition via route (1) is thermodynamically
most favorable; however, this version is of the least
interest for the implementation of other reactions. The
most thoroughly studied process is decomposition to
carbon monoxide and methyl alcohol (route (2)), i.e.,
decarbonylation that occurs in the presence of cata-
lysts based on transition metal compounds [11–15].
The catalytic decomposition of MF in the presence of
water (a variety of the water-gas shift reaction) leads to
the formation of a gas mixture, the main components
of which are carbon monoxide and hydrogen (3). The
presence of water in the reaction system ensures the
occurrence of the following stages of decomposition of
the ester [16]:
It was found that the fraction of hydrogen in the
mixtures varies from 45 to 90% depending on the
nature of the metal and the amount of water added
(Table 1). Thus, for the ruthenium complexes, the
fraction of hydrogen increases from 15 to 54% at a
slight level of excess water and approaches 81% with
high water content. A decrease in the water content,
conversely, leads to a decrease in the hydrogen content
to 46% (Table 1, entries 1–3). The activity of the rho-
dium and cobalt complexes in decomposition is sig-
nificantly lower; however, in this case, the amount of
produced hydrogen is also significant. For the cobalt
complexes, at high water content, this value is as high
as 90% (entries 5, 6).
(2)
(4)
HCOOCH3 → CO + CH3OH,
CO+H2O CO2 H2,
The data suggest that the hydrogen generation pro-
cess involves not only carbon monoxide, but also the
produced methanol. It should be noted that the for-
→
+
(5) mation of methanol owing to the occurrence of steam-
HCOOCH3 + H2O → HCOOH + CH3OH,
PETROLEUM CHEMISTRY Vol. 59 No. 4 2019

414
GORBUNOV et al.
Table 1. Methyl formate decomposition in the presence of transition metal complexes and salts without the addition of
ligands at different MF/water ratios
[HCOOCH3]/[H2O]
Pressure at Troom, MPa
Н2 content, %
No.
Catalyst
MF conversion, %
1
Ru3(CO)12
8
21
8
81
54
46
46
90
90
2.28
11
1.0
3.0
2
Ru3(CO)12
Ru3(CO)12
Rh(acac)(CO)2
Co(acac)3
3
20
1.0
4
12
2
11
<0.5
<0.5
<0.5
5*
6
2.85
2.85
Co(acac)3
2
Experimental conditions: MF, 2.0 mL (0.032 mol); Ru (CO) , 0.016 mmol; Rh(acac)(CO) , 0.004 mmol; Co(acac) , 0.06 mmol;
3
12
2
3
180°C; and 2 h. *T = 200°C.
to-water conversion under relatively mild conditions position route. Decarbonylation is not the first stage
has long been known. According to [17], the reaction
any longer; the first stage is the MF hydrolysis to
methanol and formic acid:
CH3OH + H2O → CO2 + 3H2
CH3OC(O)H + H2O ꢀ HCOOH + CH3OH.
is characterized by a negative change in the free energy
(−30 kJ/mol), unlike the conventional dehydrogena-
tion of methanol. This reaction is catalyzed by both
rhodium and ruthenium complexes; at temperatures
above 150°C, the hydrogen formation rates are fairly
high. In addition, at high temperatures, methanol
dehydrogenation can also take place; however, in the
absence of ligands, it typically occurs at a relatively low
rate [18]. It should also be noted that these reactions
still cannot provide an explanation to the fact that the
hydrogen content in the mixture is more than 66%; to
obtain this value, one mole of carbon dioxide should
be bound by one mole of hydrogen.
The kinetics of MF conversion at different tem-
peratures was also studied. According to the data in
Fig. 2, decomposition occurs at a high rate both in the
absence of water and in the presence of small amounts
of water. In this case, the maximum pressure is
achieved even within 60–70 min. In addition, an
increase in the catalyst content leads to an increase in
the total yield of gaseous products; however, the rate of
pressure rise slightly decreases. This finding is appar-
ently attributed to the fact that an increase in the cata-
lyst content provides the presence of several MF
decomposition routes. An increase in temperature
from 180 to 200°C leads to an abrupt increase in both
the reaction rate and the final pressure in the system,
which increases almost by 25%.
Formic acid undergoes decomposition to hydrogen
and carbon dioxide in the presence of ruthenium cat-
alysts and to water and carbon monoxide under the
action of temperature. Thus, the water-gas shift reac-
tion largely occurs via the formic acid dehydrogena-
tion:
CO2 + H2
HCOOH
CO + H2O
In addition, it can be directly catalyzed by ruthe-
nium complexes without the formation of formic acid.
There exist process schemes involving the formation of
Ru–H compounds and the proton abstraction from
water. It should be noted that, according to the pub-
lished data, both mononuclear and polynuclear ruthe-
nium complexes can be involved in the reaction via
several routes; this feature significantly complicates
the process mechanism [19–21].
The effect of a number of parameters on the cobalt-
catalyzed decomposition of MF was also studied
(Table 2).
An increase in the catalyst concentration leads to
an increase in the MF conversion and a slight decrease
in the fraction of hydrogen, although the hydrogen
content is significantly higher than the fraction of 66%
characteristic of ordinary stoichiometry. This finding
indicates the occurrence of carbon binding to nongas-
eous compounds containing several oxygen atoms per
carbon atom. A decrease in the amount of water leads
to an increase in the hydrogen content; a simultaneous
decrease in the catalyst concentration leads to a
decrease in the conversion and the fraction of hydro-
gen.
The addition of water leads to a decrease in the total
rate; at an MF/water ratio of 11, the pressure increases
more slowly than it does at MF/water = 20. In the lat-
ter case, the shape of the kinetic curve resembles the
shape of the curves recorded in the absence of water,
whereas in the second case, the time dependence of
pressure is an almost rectilinear; that is, it indicates the
occurrence of a zeroth-order reaction.
Apparently, in this case, an increase in the amount
It should be noted that with an increase in the reac-
of water can cause a change in the general MF decom- tion time, the fraction of hydrogen in the final mixture
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CATALYTIC DECOMPOSITION OF METHYL FORMATE
25
415
20
15
10
5
0.025 mmol of Ru3(CO)12, 200°C
0.025 mmol of Ru3(CO)12, 180°C
0.016 mmol of Ru3(CO)12, 180°C
0.016 mmol of Ru3 CO)12, 0.03 mL of H2O, 180°C
(
0.016 mmol of Ru3(CO)12, 0.05 mL of H2O, 180°C
0
50
100
150
200
250
Time, min
Fig. 2. Time dependence of the pressure of the gas mixture during methyl formate decomposition under different conditions
(0.032 mol of MF).
slightly decreased; this finding suggests the following:
on one hand, hydrogen undergoes a reaction to form
nongaseous products; on the other hand, the evolu-
tion of carbon monoxide and carbon dioxide increases
and this process is not accompanied by the water-gas
shift reaction because of a significant decrease in the
water concentration in the system. This trend is
observed at various catalyst concentrations (Table 3);
it is much more pronounced with an increase in the
catalyst concentration.
Modification of the proposed catalyst systems for
MF decomposition was conducted by adding a num-
ber of ligands. The choice of the ligands was based on
the different electron-donating abilities of these sys-
tems and the different degrees of steric hindrances.
Data on the MF decomposition without water admix-
ture in the presence of the rhodium and ruthenium
complexes are shown in Table 4.
It should be noted that the addition of ligands has a
negligible effect on the amount of hydrogen produced.
In addition, the MF conversion is low, except for the
case of the rhodium complex with phosphine exhibit-
ing a high electron-donating ability—tricyclohexyl-
phosphine—taken in a significant excess; this complex
was highly active. In addition, this complex provided
the highest proportion of hydrogen (35%). Taking into
account the absence of water, the most probable reac-
tion in this case is methanol dehydrogenation to form-
aldehyde; in addition, the reaction apparently pro-
It can be assumed that the decrease in the hydrogen
content is associated with the formation of a larger
fraction of carbonyl complexes of cobalt in the system
over time. In fact, the use of cobalt nitrate as a source
of the metal leads to the formation of 45% of hydrogen
in the system, while the use of cobalt carbonyl provides
an increase in the MF conversion and the presence of
20% of hydrogen in the gas mixture.
Table 2. Methyl formate decomposition in the presence of cobalt acetylacetonate
[HCOOCH3]/[H2O]
[HCOOCH3]/[metal]
Н2 content, %
MF conversion, %
2.85
2.85
2.85
2.85
2.85
3.8
2280
1140
760
570
450
450
450
760
1
2
5
10
11
10
10
4
90
90
89
85
70
90
90
65
5.7
3.8
Experimental conditions: MF, 2.0 mL (0.032 mol); 200°C; and 2 h.
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416
GORBUNOV et al.
Table 3. Methyl formate decomposition in the presence of
cobalt acetylacetonate
hydrogen in the system—up to 86%—is observed,
while the fraction of carbon monoxide is not high.
Н2
content,
%
Data on the effect of excess ligand on the MF
decomposition process are shown in Table 6. An
increase in the ligand/metal ratio from 10 to 20 leads
to a slight decrease in activity, particularly with an
increase in the fraction of water in the system. At the
same time, the fraction of hydrogen significantly
decreases. During reaction at a ligand/metal ratio
of 10, the fraction of hydrogen was 75%, whereas
during reaction with the doubled amount of the
ligand, the hydrogen content was as low as 55%.
Apparently, at a large level of excess phosphine, both
the water-gas shift reaction and the methanol dehy-
drogenation reaction are suppressed. As a conse-
quence, the decrease in the pressure and MF conver-
sion is not extremely abrupt and the fraction of hydro-
gen, even at a large amount of water, is not high. In this
case, a portion of the gas is carbon monoxide, rather
than carbon dioxide.
Time,
h
[HCOOCH3]/[H2O] [HCOOCH3]/[metal]
2.85
2.85
2.85
2.85
2.85
1140
1140
760
760
760
2
3
2
4
6
90
80
89
71
61
Experimental conditions: MF, 2.0 mL (0.032 mol); 200°C.
ceeds to a significant extent. At least 30% of the total
amount of methanol undergoes dehydrogenation,
which is followed by the decarbonylation of the result-
ing formaldehyde. These data are confirmed by pub-
lished data on methanol dehydrogenation catalyzed by
rhodium complexes under heating.
Interesting data were obtained in studying the
dependence of conversion and hydrogen content in
the system on the nature of the ligand used (Table 7).
With a decrease in the MF/water ratio (Table 5), a
significant increase in the pressure of the final gas
mixture is observed; a decrease in the ratio from 11 to
5.5 leads to an abrupt pressure jump in the system and,
accordingly, a multiple increase in the MF conversion.
It should be noted that the complexes with phos-
phorus-containing ligands exhibited high activity.
Complexes with amines were significantly less active
in MF decomposition. It is worth noting that the
bidentate ligand of the XANTHOS type exhibits rela-
tively high activity; it provides a relatively high MF
conversion at a fairly high hydrogen content in the
mixture.
It should be noted that with an increase in the
amount of water, the proportion of hydrogen in the gas
mixture also abruptly increases. At a ratio of 5.5, the
hydrogen content corresponds to the equilibrium
amount for MF decomposition and the formation of a
carbon dioxide–hydrogen mixture, whereas at a ratio
close to unity, the system contains 86% of hydrogen.
Analysis of the liquid phase for methyl alcohol shows
that the final pressure in the system corresponding to
the total amount of this substance should be almost
2 times higher. This finding confirms our hypothesis
that, during the reaction, a portion of the formed car-
bon dioxide is bound to form nongaseous compounds
that are soluble in water and/or methanol. An increase
in the amount of water contributes to this process. As
Data on the use of the rhodium complexes in the
MF decomposition reaction in the presence of water
additives are shown in Table 8.
For further research, it was of particular interest to
study the MF decomposition in a mixed system con-
taining both a rhodium complex and a ruthenium
complex (Table 9). It should primarily be noted that
the system containing the two metals and tricyclohex-
ylphosphine is significantly more active than similar
monometallic catalysts.
A synergistic effect is
observed with an increase in the MF conversion to
a consequence, an abrupt increase in the amount of 38% versus 19 and 30% provided by the pure rhodium
Table 4. Methyl formate decomposition with the addition of ligands in an anhydrous medium
Pressure at Troom, MPa
Н2 content, %
No.
Catalyst
Ligand
[L]/[metal]
MF conversion, %
1
2
3
4
5
6
Ru3(CO)12
PCy3
10.00
10.00
10.00
40.00
40.00
40.00
<0.5
<0.5
<0.5
10.0
<0.5
<0.5
3
0.3
1
<1
2
Ru3(CO)12
PPh3
Ru3(CO)12
HNEt2
PCy3
12
35
24
<5
Rh(acac)(CO)2
Rh(acac)(CO)2
Rh(acac)(CO)2
70
1
PPh3
HNEt2
1
Experimental conditions: MF, 2.0 mL (0.032 mol); Ru (CO) , 0.016 mmol; Rh(acac)(CO) , 0.004 mmol; ligand, 0.16 mmol; 180°C;
3
12
2
and 2 h.
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CATALYTIC DECOMPOSITION OF METHYL FORMATE
417
Table 5. Methyl formate decomposition in the presence of ruthenium complexes with triphenylphosphine as a function of
the MF/water ratio
[HCOOCH3]/[H2O]
Pressure at Troom, MPa
Н2 content, %
MF conversion, %
11.00
5.50
2.75
1.00
–
4
18
28
48
47
50
75
86
2.0
4.0
7.0
Experimental conditions: MF, 2.0 mL (0.032 mol); Ru (CO) , 0.016 mmol; PPh , 0.16 mmol; 180°C; and 2 h.
3
12
3
Table 6. Methyl formate decomposition in the presence of ruthenium complexes with triphenylphosphine as a function of
the ligand/metal ratio
[HCOOCH3]/[H2O] Pressure at Troom, MPa
Н2 content, %
[L]/[metal]
MF conversion, %
10.00
20.00
10.00
20.00
11.00
11.00
2.75
<0.5
<0.5
4.0
4
4
28
21
47
34
75
55
2.75
3.0
Experimental conditions: MF, 2.0 mL (0.032 mol); Ru (CO) , 0.016 mmol; 180°C; and 2 h.
3
12
and pure ruthenium systems, respectively. In this case, whereas for the phosphine complexes, it does not
the hydrogen content in the mixture is as low as 13% exceed 75% at the same ratio; at a ratio of 5.5, the frac-
(about 50% for the monometallic systems under simi- tion of hydrogen is 75%; for the triphenylphosphine–
lar conditions). This fact means that the system con- ruthenium system, it is 50%.
tains a fairly high amount of carbon monoxide, which
Data on the MF decomposition in a mixed system
is favorable for the occurrence of the hydroformylation
in the presence of the triphenylphosphine ligand are
reaction.
shown in Table 10. As in the case of the ruthenium sys-
tems, an increase in the proportion of water leads to an
In the case of using sulfonated triphenylphosphine,
increase in the hydrogen content in the gaseous prod-
which is a water-soluble ligand, the MF conversion is
ucts and an increase in the MF conversion.
relatively high and the amount of hydrogen in the sys-
tem is significant. In this case, owing to the high water
It is also significant that unlike the case of the
solubility of the ligand, the rhodium and ruthenium ruthenium system, an increase in the amount of the
complexes are present almost completely in the aque- ligand does not lead to a decrease in the hydrogen
ous phase; this feature provides an abrupt increase in selectivity and the MF conversion. Conversely, the
the rates of reactions involving water and the binding conversion increases almost by a factor of 1.5, while
of carbon dioxide in an aqueous medium. At an the fraction of hydrogen in the system remains high.
MF/water ratio of 2.75, the amount of produced Apparently, this fact is attributed to the establishment
hydrogen in the gas mixture is more than 90%, of a system of equilibria between the phosphine com-
Table 7. Methyl formate decomposition in the presence of various ruthenium complexes
[HCOOCH3]/[H2O]
Н2 content, %
Ligand
[L]/[metal]
MF conversion, %
PPh3
10.00
10.00
10.00
10.00
10.00
2.00
2.75
11.00
2.75
28
4
75
47
70
38
87
77
62
26
PPh3
PCy3
30
25
40
32
4
PCy3
11.00
2.75
P(OPh)3
XANTРHOS
HNEt2
2.75
11.00
11.00
10.00
10.00
NEt3
7
Experimental conditions: MF, 2.0 mL (0.032 mol); Ru (CO) , 0.016 mmol; 180°C; and 2 h.
3
12
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GORBUNOV et al.
Table 8. Methyl formate decomposition catalyzed by rhodium complexes in the presence of water
Pressure
at Troom, MPa
MF conversion,
%
[HCOOCH3]/ [H2O]
Н2 content, %
No.
Ligand
[L]/[metal]
1* PCy3
2* PPh3
3* NEt3
4* PPh3
40.00
40.00
40.00
40.00
11.00
11.00
11.00
2.75
2.5
<0.5
2.0
19
5
50
45
44
76
17
3.5
24
HNEt2 (P/N=3)
Experimental conditions: MF, 2.0 mL (0.032 mol); * Rh(acac)(CO) , 0.004 mmol; ** [RhL ]BF , 0.01 mmol; 180°C; and 2 h.
2
2
4
Table 9. Methyl formate decomposition in the presence of the Ru3(CO)12–Rh(acac)(CO)2 bimetallic catalyst system
[HCOOCH3]/[H2O] Pressure at Troom, MPa
Н2 content, %
Ligand
MF conversion, %
PCy3
11.00
11.00
5.50
2.75
2.75
2.75
5.0
<0.5
2.0
4.0
4.5
35
1
13
20
75
92
85
75
PPh3
TPPTS
TPPTS
P(OPh)3
17
28
32
34
PPh3 + HNEt2
4.8
Experimental conditions: MF, 2.0 mL (0.032 mol); Ru (CO) , 0.016 mmol; Rh(acac)(CO) , 0.004 mmol; PPh , 0.16 mmol; P(ОPh) ,
3
12
2
3
3
0.16 mmol; HNEt , 0.48 mmol; TPPTS, 0.2 mmol; 180°C; and 2 h.
2
Table 10. Methyl formate decomposition in the triphenylphosphine–Ru3(CO)12–Rh(acac)(CO)2 mixed system
[HCOOCH3]/[H2O] Pressure at Troom, MPa
Н2 content, %
Ligand
MF conversion, %
11.00
5.50
2.75
2.75
<0.5
2.0
1
17
21
32
20
55
77
77
PPh3
PPh3
PPh3
3.0
*
PPh3
4.5
Experimental conditions: MF, 2.0 mL (0.032 mol); Ru (CO) , 0.016 mmol; Rh(acac)(CO) , 0.004 mmol; PPh , 0.16 mmol; and
3
12
2
3
* PPh , 0.32 mmol.
3
plexes of rhodium and ruthenium in the system and formylation, hydroformylation–acetalization, and
the difference in the activity and selectivity of these hydroaminomethylation reactions.
complexes in MF decomposition: the rhodium com-
plexes, for the most part, are responsible for hydrogen
selectivity, while the ruthenium component of the sys-
tem is largely responsible for the decomposition rate.
ACKNOWLEDGMENTS
This work was supported by the Russian Founda-
tion for Basic Research, project no. 18-33-01227.
CONCLUSIONS
The experimental data obtained in this study sug-
gest that along with the MF decomposition to metha-
nol and carbon monoxide and the water-gas shift reac-
tion, a number of processes occur that significantly
complicate the decomposition and make it possible to
control the composition of the gaseous mixture. In
continuation of this research, we are going to explore
the possibility of using methyl formate as an alterna-
tive source of synthesis gas for running the hydro-
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