Efficient methanol carbonylation to methyl acetate catalyzed by a cyclic(alkyl)(amino)carbene iridium complex

Article abstract of DOI:10.1039/d0cy00054j

An efficient cyclic(alkyl)(amino) carbene iridium complex (C-2) was developed for methanol carbonylation to methyl acetate (MA) directly. Compared with previous results, methanol carbonylation to MA catalyzed byC-2was performed quite well at a low temperature (120 °C). The reaction showed excellent selectivity toward MA (96%) even when the conversion was high (81%). The reaction processes were also investigated by stoichiometric experiments and theoretical calculations.

Full text of DOI:10.1039/d0cy00054j

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ISSN 2044-4761
PAPER
Chaoqiu Chen, Yong Qin et al.
Highly dispersed Pt nanoparticles supported on carbon
nanotubes produced by atomic layer deposition for hydrogen
generation from hydrolysis of ammonia borane
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DOI: 10.1039/D0CY00054J
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Efficient Methanol Carbonylation to Methyl Acetate Catalyzed by
Cyclic(alkyl)(amino)carbene Iridium Complex †
Dejin Zhang,ab Guoqiang Yang,a Yue Zhao, a Shouyan Shao,c Guisheng Zhu,c Peijun Liu,c Jia Liu, a
Xingbang Hu* a and Zhibing Zhang*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
An efficient cyclic(alkyl)(amino) carbene iridium complex (C-2) was oC. A Rh catalyst immobilized over cross-linked polymer was
o
first developed for the methanol carbonylation to methyl acetate reported for the methanol carbonylation at 120 C. However,
10
(MA) directly. Comparing with previous results, the methanol the MA and AC yields were only 40 and 10% respectively.
carbonylation to MA catalyzed by C-2 performs quite well at lower Hence, developing more reactive catalyst with high MA
o
temperature (120 C). The reaction shows excellent selectivity of selectivity for the methanol carbonylation at lower
MA (96%) even when the conversion is high (81%). The reaction temperature is still full of challenges.
processes were also investigated by stoichiometric experiments
and theoretical calculations.
Replacing one of the electronegative and π-donor amino
substituents of tranditional N-heterocyclic carbenes (NHCs) by
a σ-donating but not π-donating alkyl group results in a new
carbene, Cyclic (alkyl)(amino)carbene (CAACs). CAACs are
more nucleophilic (σ-donating) but also more electrophilic (π-
Carbon monoxide (CO), as a highly toxic gas, is produced in
large quantities in many chemical processes, such as methanol
cracking to produce hydrogen, water gas reaction, et al.
Conversion of CO into useful chemicals is receiving more and
more research interests.1 Many important and interesting
11
12
13
accepting) than NHCs.
The CAAC-Au,
CAAC-Ru
and
14
CAAC-Cu have been revealed to be excellent catalysts for
hydrogenation, dehydrogenation, hydroamination, and click
reaction. Herein, we reported the first synthesis of
cyclic(alkyl)(amino) carbene iridium (C-2) and an efficient
methanol carbonylation to MA catalyzed by C-2.
reactions use CO as starting material, such as carbonylation,
2a,2b
hydroformylation,2c,2d
hydroesterification,2e,2f
hydrocarboxylation2h and so on.
Methanol carbonylation is absolutely one of the most
important routes, which has produced more than 80% acetic
3
acid (AC) in the world. Methyl acetate (MA) is an important
KHMDS
N
Dipp
downstream product of AC which has been widely used as
solvent, raw material of spices and leather, et al. 4 Usually, MA
is produced by the esterification between AC and methanol.
Direct synthesis of MA by the methanol carbonylation can
[IrCl(COD)]2
N+
Dipp
-78 oC to rt
Ir
BF4-
Cl
shorten the technological process. Many excellent works have
(75%)a
C-1
C-2
5-10
been performed in this field.
However, though different
noble metal based catalysts have been developed for the
methanol carbonylation, the reaction temperature is still quite
high, such as 300 oC for Rh/Na-ZrO2 catalyst, 5 240 oC for Au/C,
rt
CO
6
Ir−La/C, or Rh-bpim-CTF, 190-200 oC for Ir(CO)3I, Rh-POL-
3, 7
o
2BPY, Rh-XHPW/SiO2, Rh-POL-PPh3, or Rh-CN,
180 C for
N
N
CH3I
Dipp
Rh(CO)2I2, 8 150 oC for Ir-pincer or RhCl(SPAN-PPh2)(CO). 9 Only
few research achieved the methanol carbonylation below 150
Dipp
OC
I
-78oC to rt
OC Ir Cl
H3C
C-4
Ir Cl
a School of Chemistry and Chemical Engineering, Nanjing University, Nanjing
210093, P. R. China. E-mail: huxb@nju.edu.cn, zbzhang@nju.edu.cn
b School of Chemistry and Chemical Engineering, Suzhou University, Suzhou,
Anhui 234000, P. R. China.
CO
(83%)a
CO
(87%)a
C-3
c Jiangsu SOPO (Group)CO.,LTD, Zhengjiang, 212006,P. R. China.
Fig. 1 The synthesis of C-2 and its reactivity. Dipp=2,6-
†Electronic
DOI: 10.1039/x0xx00000x
These authors contributed equally to this work.
Supplementary
Information
(ESI)
available.
See
diisopropylphenyl. a Isolated yield.
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under 180, 200, and 240 oC respectively. For the reaction
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C-2 was synthesized according to similar procedure of CAAC- catalyzed by C-2, even when water waDsOinI:t1r0o.1d0u39c/eDd0CinYt0o00t5h4eJ
14a, 14b
Cu reported by Bertrand and us,
iminium tetrafluoroborate
bis(trimethylsily) amide
using diethyl cyclic reaction system, 95% selectivity of MA still can be obtained at
salt
(KHMDS)
(C-1),
and
potassium 120 oC (Entry 5).
chloro(1,5- Table 1. The methanol carbonylation to MA.
cyclooctadiene)iridium(I) dimer ([IrCl(COD)]2) as starting
materials (Fig. 1). After work up, C-2 was isolated as a yellow
solid in 75% yield. This compound is air and moisture-stable. It
can be stored for weeks with no decomposition. The structure
of C-2 was confirmed by single-crystal X-ray diffraction (Fig. 2),
Entr
y
Temp.
(oC)
Cat. dosage
(%mol)
Sel. of MA
(%)
Con. (%)
100
120
0.1
0.1
55
81
93
96
1
2
15
NMR and HRMS. The Ir-Cl and Ir-Ccarbene distances in C-2 are
2.392 and 1.995 Å, respectively. The Ccarbene exhibits a chemical
shift at 261.2 ppm in 13C NMR, which is the characteristic of
carbene based on CAAC. 12-14
3
4
83
87
80
70
76
72
61
58
79
79
68
95
83
80
81
100
99
94
150
180
120
120
120
120
120
120
120
0.1
0.1
When CO was introduced into the solution of C-2 at room
temperature, carbonylation of C-2 happens with 87% isolated
yield of C-3. Single-crystal X-ray diffraction analysis shows that
C-3 is CAAC-Ir binding with two CO (Fig. 2). Comparing with the
data of C-2, the Ir-Ccarbene distance in C-3 is enlarged to 2.086 Å
and the 13C NMR chemical shift of Ccarbene moves to 253.2 ppm.
When CH3I and C-3 were mixed, a clear move of CCH3I chemical
shift was observed from -23.2 to 1.2 ppm, suggesting a
reaction between CH3I and C-3 to produce C-4. Besides,
comparing with the IR of C-3, a significant characteristic peak
of methyl was found at 1259 cm-1 after the oxidative addition
of CH3I, which also demonstrated the formation of C-4 (see Fig.
S3 in ESI).
5a
6
0.1
0.05
0.05
0.05
0.1
7b
8c
9d
10e
11f
0.1
0.1
General condition: 125 mmol methanol, catalyst (C-2),
PCO=2 MPa, 120 ℃ , 0.2 mL CH3I, 24 h. Conversion of
methanol and selectivity were determined by GC and GC-
MS. Selectivity of MA=MA/(MA+DME+AC). [a] 0.4 mL H2O
was added. [b] 0.05 mol% RuCl3 was added. [c] 50 mg LiCl
was added. [d] 10 mmol methanol, 5mL THF as solvent.
[e] 10 mmol methanol, 5mL toluene as solvent [f] C-3 was
used as catalyst.
N
N
Cl
Ir
Ir
Cl
C
O
C
C-3
C-2
100
75
50
25
0
100
80
60
40
20
0
Fig. 2 The X-ray structure of C-2 (CCDC:1958720) and C-3
(CCDC:1969354). Hydrogen atoms are omitted for clarity.
Above stoichiometric reaction results indicate that C-2 may
be efficient catalyst for the methanol carbonylation. To
explore the catalytic ability of C-2, the methanol carbonylation
was performed at different temperature under 2 Mpa of CO
(Entries 1-4, Table 1). Though the reaction can work at 100 oC,
the conversion is not good. Under 120 oC, a temperature being
obviously lower than those reported in previous researches, 5-8
a good conversion of methanol and excellent selectivity of MA
can be obtained (Entry 2). Further increasing the temperature
results in better conversion (Entries 3 and 4). However, the MA
Conversion of methanol
Selectivity of DME
Selectivity of MA
Selectivity of AC
5
10
15
20
25
o
selectivity becomes quite poor at high temperature (180 C)
because of the decomposing of MA to AC (see Table S1 in ESI).
Hence, the high reaction temperature in previous researches
Time/h
Fig. 3 The conversion and selectivity of the reaction at
different time. MA: Methyl acetate; DME: Dimethyl Ether; AC:
acetic acid. Reaction conditions: 0.1% mol C-2, 125 mmol
methanol, PCO=2 MPa, 120℃, 0.2mL CH3I.
5-8
should be one of the reasons inducing low MA selectivity.
8
3
6d
For examples, the MA selectivities are 74 , 50 , and 44%
2 | J. Name., 2012, 00, 1-3
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CH3COI by C-I bond formation via TS3 (barrier: 15.5 kcal/mol).
The conversion and selectivity of the reaction at different An additional CO binding to C-6 can regenerateVitehweArtcicaletOanlylinset
DOI: 10.1039/D0CY00054J
o
time under 120 C were plotted in Fig. 3. At the beginning of and release CH3COI. The reaction between CH3COI and CH3OH
18
the reaction, it produced less than 10% dimethyl ether (DME). to produce MA and CH3I is quite easy under mild condition
A clear decrease of DME and increase of the MA selectivity and this process is highly exothermic (-21.5 kcal/mol). The
was observed as the reaction proceeds. It suggests that rate-determining step in the whole process is the
carbonylation of DME to MA happens. 4a, 16 A direct evidence transformation from C-4 to C-5 with a barrier of 17.0 kcal/mol.
was obtained by the experiment using DME as substrate in the
absence of methanol and 100% selectivity of MA was obtained
in the carbonylation of DME (see Scheme S1 in ESI). It is
Conversion
Selectivity
100
80
60
40
20
0
interesting to find that there had almost no AC produced
during the reaction (Fig. 3). Comparing with previous results, 5-
9
the methanol carbonylation to MA catalyzed by C-2 shows
excellent selectivity when the conversion is high.
Reducing the amount of catalyst leaded to the decrease of
both conversion and selectivity of MA (Entry 6, Table 1),
because there has more DME produced. Previous research
had shown that adding Ru compound into the Ir(CO)3I can
obviously enhance the reaction rate of methanol carbonylation.
7a
A bimetallic catalyst system including 0.05 % mol RuCl3 and
0.05 % mol C-2 was adopted here and slight increase on the
conversion was observed (Entries 6 and 7). Adding salt is
9a
another method for improving the catalytic reactivity. LiCl
was introduced into the reaction system as an additive.
However, there has no remarkable difference (Entries 6 and 8).
It is worth noticing that when THF was added as solvent,
almost 100% selectivity of MA can be obtained with 61%
conversion of methanol (Entry 9). Similarly, when toluene was
used as solvent, 99% selectivity of MA was obtained with 58%
conversion of methanol (Entry 10). The results were obtained
at a quite lower methanol concentration which is benefit for
increasing the selectivity.
Longer reaction time did not give significant change in the
conversion (see Table S2 in ESI). After the reaction of methanol
carbonylation, the structure of CAAC-Ir has been investigated
by NMR and it was found that the catalyst has decomposed.
These results suggest that the catalyst is inactive after
degradation and the CAAC-Ir should be the true active species
in the methanol carbonylation.
To better evaluate the catalytic ability of C-2, the methanol
carbonylation catalyzed by different Ir-complexes were
investigated under the same condition (Fig. 4). Though the
commercial available IrCl3 showed comparable MA selectivity
to C-2, its catalytic reactivity was too low. [IrCl(COD)]2, the
precursor for the synthesis of C-2, gave poor methanol
conversion and MA selectivity. Obviously, C-2 gave the best
conversion and selectivity of MA among the catalysts
investigated here. Especially, a typical (NHC)Ir(CO)2Cl was
synthesized and characterized (see ESI for detail). Comparing
with C-2, a lower catalytic performance was obtained in the
presence of (NHC)Ir(CO)2Cl. Previous research has revealed
that the HOMO-LUMO gap of CAAC is smaller than that of NHC.
This may be the reason why CAAC-Ir is more reactive.11d
D
E
C
F
A
B
Catalysts
Fig. 4 The methanol conversion and MA selectivity of
carbonylation catalyzed by different catalysts. Reaction
conditions: 0.1% mol catalyst, 125 mmol methanol, PCO=2
MPa, 120 oC, 0.2 mL CH3I, 24 h. Catalyst: (A) IrCl3, (B) Iridium
dicarbonyl
pentanedionate,
(C)
Carbonyl
bis(triphenylphosphine) iridium chloride, (D) [Ir(COD)Cl]2, (E) C-
2, (F) (NHC)Ir(CO)2Cl.
C-6
C-5
(a)
N
N
Dipp
Dipp
Cl
Cl
O
21.6
C-2
Ir
O
C
Ir CO
CO
C
CH3I
10.6
H3C
I
I
H3C
0.1
TS1
0.0
-2.3
-1.6
CO
-14.9
TS3
C-3
TS2
C-6
-15.4
-19.3
C-3
C-5
CH3OH
C-4
+CH3COI
(b)
-36.4
CH3CO2CH3
+CH3I
2.401
3.180
2.921
2.414
2.187
1.905
1.879
TS1
TS3
TS2
Fig. 5 The energy profile (in kcal/mol) for the carbonylation of
CO obtained by PCM calculation using B3LYP-D3(BJ)/6-
311++G**/LANL2DZ method.
A
theoretical calculation was further performed to
investigate the reaction pathway of this reaction. The reaction
between C-2 and CO to produce C-3 is highly exothermic (-21.6
kcal/mol). According to previous research, the oxidative
In summary, an efficient cyclic(alkyl)(amino) carbene iridium
(CAAC-Ir) complex was first developed for the methanol
17
addition of CH3I follows a SN2-type mechanism.
Similar
mechanism is adopted here and a barrier of 10.6 kcal/mol was
obtained for the oxidative addition step. After that, a series of
isomerization happen, including the binding between CH3 and
CO via TS2 (barrier: 17.0 kcal/mol) and the producing of
carbonylation to methyl acetate (MA) directly. Comparing with
5-10
previous results,
the methanol carbonylation to MA
catalyzed by CAAC-Ir performed quite well at lower
temperature. At the same time, it shows excellent selectivity
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industry, its stability in the carbonylation reaction has to be
improved.
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Acknowledgement
This work was supported by National Natural Science
Foundation of China (No. 21776122, 21676134, 21878141 and
21576129) and Jiangsu Province NSF (BM2018007).
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Conflicts of interest
We have no conflicts of interest to declare.
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DOI: 10.1039/D0CY00054J
TOC：
CH3OH + CO
CH3CO2CH3
Lower temperature
Higher selectivity
Experiment and theory