Carbon dioxide hydrosilylation to methane catalyzed by zinc and other first-row transition metal salts

Article abstract of DOI:10.1246/bcsj.20190203

We accomplished zinc catalyzed hydrosilylation of carbon dioxide (CO₂) to silyl formate (C^+II), bis(silyl)acetal (C⁰), methoxysilane (C^1II), and finally methane (C^1IV). Among several zinc salts, we found that Zn(OAc)₂ with ligand 1,10-phenanthroline was the best. A turnover number of 815000 was achieved using the zinc catalyst to yield C^+II. Unexpectedly, we observed the generation of CO from CO₂ and hydrosilane for the first time. In addition to Zn, other first-row transition metals (Mn, Fe, Co, Ni, and Cu) also served as Lewis acid catalysts for CO₂ hydrosilylation, regardless of the nature of the metal.

Full text of DOI:10.1246/bcsj.20190203

Document type: Article
Carbon Dioxide Hydrosilylation to Methane Catalyzed
by Zinc and Other First-Row Transition Metal Salts
Qiao Zhang, Norihisa Fukaya, Tadahiro Fujitani, and Jun-Chul Choi*
National Institute of Advanced Industrial Science and Technology (AIST),
1-1-1 Higashi, Tsukuba Central 5, Tsukuba, Ibaraki 305-8565, Japan
E-mail: junchul.choi@aist.go.jp
Received: July 12, 2019; Accepted: September 6, 2019; Web Released: September 13, 2019
Jun-Chul Choi
Jun-Chul Choi received his Ph.D. degree from Tokyo Institute of Technology in 1998 (Prof. Kohtaro
Osakada). He joined the National Institute of Advanced Industrial Science and Technology (AIST) as a JST
postdoctoral fellow in 1998. Currently, he is the leader of Catalyst Design Team at Interdisciplinary Research
Center for Catalytic Chemistry at AIST, and holds the position of Associate Professor at University of
Tsukuba. His research interests include the development of efficient synthetic reactions, especially the
utilization of fundamental molecules such as carbon dioxide, hydrocarbons, and water. He is also interested
in designing organic-inorganic hybrid catalysts.
Abstract
We accomplished zinc catalyzed hydrosilylation of carbon
+
II
0
dioxide (CO ) to silyl formate (C ), bis(silyl)acetal (C ),
2
methoxysilane (C II), and finally methane (C¹IV). Among
¹
several zinc salts, we found that Zn(OAc) with ligand 1,10-
2
phenanthroline was the best. A turnover number of 815000 was
Scheme 1. Catalytic CO2 hydrosilylation.
+II
achieved using the zinc catalyst to yield C . Unexpectedly,
we observed the generation of CO from CO and hydrosilane
for the first time. In addition to Zn, other first-row transition
metals (Mn, Fe, Co, Ni, and Cu) also served as Lewis acid
to formic acid level is the most facile, yielding silyl formate
2
+II
14­26
27­36
(HCOOSiR , C ) when noble,
organocatalysts are employed. The further reduction of CO
non-noble metal,
and
3
3
7
2
0
22­24,38­44
catalysts for CO hydrosilylation, regardless of the nature of the
to yield bis(silyl)acetal (CH (OSiR ) , C ),
methoxy-
2
2
3 2
¹
II 22­24,34,39,41,45­51
metal.
silane (CH3OSiR3, C ),
or methane (CH4,
¹
IV 22,39,41,43,47,48,52­59
C
)
has also been reported, in addition to
6
0­67
Keywords: Carbon dioxide j Hydrosilylation
j
Zinc
mechanistic studies into CO hydrosilylation.
2
In the context of previous work carried out in this area, we
considered a number of issues that required addressing. For
1
. Introduction
example, although all CO hydrosilylations reported to date
2
Carbon dioxide (CO ) is a non-toxic, non-flammable, and
require a catalyst, a number also require the use of noble
2
1
4­19,21­26
inexpensive gas, and it can be applied as a C1 synthon for the
preparation of a range of valuable chemicals.1 Although the
synthesis of organic carbonate, urea, or carbamate from CO2
does not involve changes in the oxidation state of carbon, the
metals
and both the ligands and organocatalysts
­5
employed tend to be complicated. The use of a non-precious
catalyst based on readily available ligands is therefore desir-
able. In addition, only 25% of studies in this field reported full
transformation of CO to formic acid, formaldehyde, methanol,
hydrosilylation of CO2 to CH . Furthermore, although the
2
4
+II
0
¹II
and methane requires the reduction of carbon to C , C , C
and C , respectively. For such processes, hydrosilanes,
,
properties of the catalyst metal cations have been examined, the
interactions between counteranions and hydrosilanes received
little attention.
¹
IV
hydroboranes, and H can be employed as reductants for
2
6­13
CO2.
With hydrosilane, the reduction of CO is facile, as
We previously reported CO as a C1 building block in
2
2
6
8­72
this process involves the cleavage of a weak Si­H bond,
followed by the formation of a stronger Si­O bond.
organic synthesis
based on a catalytic combination of
Zn(OAc)2 and ligand 1,10-phenanthroline (phen). In this
6
8
As indicated in Scheme 1, the products of CO2 hydro-
system, carboxylate-assisted proton abstraction from the amine
+
II
68,69,71
silylation contain four different oxidation states, including C
,
was the key step in the catalytic cycle.
Encouraged by
0
¹II
¹IV
C , C , and C . During this process, the reduction of CO2
these results, we herein report the use of a Zn(OAc) /phen
2
Bull. Chem. Soc. Jpn. 2019, 92, 1945–1949 | doi:10.1246/bcsj.20190203
© 2019 The Chemical Society of Japan | 1945

catalyst (1, Zn(OAc) :phen = 1:3) for the hydrosilylation of
(5) Detection of 13CO: Zn(OAc) (0.01 mmol, 1.8 mg),
2
2
CO . This strategy is particularly desirable as both Zn(OAc)
phen (0.03 mmol, 5.4 mg), CD CN (0.15 mL), Ph SiH (0.2
2
2
3
2
2
and phen are commercially available. Thus, we attempted the
step-by-step reduction of CO to CH with the characterization
of H, C{ H}, and C NMR spectra. Furthermore, we exam-
ined the use of other first-row transition metal acetates as
catalysts (M(OAc)2, M = Mn, Fe, Co, Ni, and Cu).
mmol, 36.8 mg) were added to a valved NMR tube, and filled
1
3
with CO to 0.25 MPa (initial pressure) at room temperature.
2
4
2
1
13
1
13
13
13
1
C NMR (100 MHz): 184 ppm (s). C{ H} NMR (100 MHz):
184 ppm (s).
3
. Results and Discussion
2
. Experimental
Initially, the catalytic ability of 1 (1:3 mixture of Zn(OAc)2
and phen) in the activation of hydrosilane was investigated.
According to the transformation indicated in Scheme 2, rapid
H/D exchange was observed between Ph SiD and PhSiH at
Materials. Unless stated otherwise, all of the chemicals
were purchased from Sigma-Aldrich, Tokyo Chemical Industry
TCI), or Wako Chemicals in the best grade, and they were
(
2
2
3
stored under N in a glovebox. Ph SiD was purchased from
25 °C over 0.5 h (Figure S1, supporting information), thereby
suggesting the formation of a Zn­H(D) intermediate. The
obtained results appeared to confirm that 1 promoted both the
rapid activation of hydrosilane and hydride exchange. Further-
more, in the presence of 1, bubbles were observed immediately
in a mixture of Ph SiD and MeOH, which suggested the
2
2
2
Santa Cruz Biotechnology. CO was purchased from Showa
2
1
3
Tansan. CO2 was purchased from Sigma-Aldrich (99.9%
atom 13C).
Instruments. The catalytic hydrosilylation reactions were
carried out in a 10 mL stainless-steel autoclave with a gas-
pressure monitor (max. 25 MPa), or in a valved NMR tube
2
2
formation of deuterated hydrogen gas (HD). Indeed, in the
1
(
V = 1 mL) produced by Norell Inc. All of the operations were
H NMR spectrum recorded in a valved NMR tube, a triplet
1
13
1
13
carried out in a glovebox under N . H, C{ H}, and C NMR
with a J value of 42.6 Hz was observed at 4.4 ppm in C D ,
2
6
6
spectra were recorded on a 400 MHz Bruker NMR spectrom-
eter at 25 °C.
which confirmed the formation of HD gas (Figure S2, support-
ing information). These results suggested that 1 was an efficient
catalyst for activating hydrosilanes.
Identifying CO Reduction Products. (1) Silyl Formate
2
+II
(C
): Zn(OAc) (0.02 mmol, 3.7 mg), phen (0.06 mmol, 10.8
Encouraged by the efficient catalytic performance of 1, we
carried out an initial investigation into the hydrosilylation of
CO using an autoclave containing a solution of Ph SiH in
2
mg), CD CN (1 mL), Ph SiH (1 mmol, 184 mg) were added to
3
2
2
an autoclave. The autoclave was sealed tightly, and filled with
2
2
2
CO to 1 MPa (initial pressure). After 24 h reaction at room
CD CN. In the presence of 2 mol% 1, silyl formate was formed
2
3
temperature, CO2 was released gently, and mesitylene was
added as an internal standard. The solution was then transferred
at 25 °C under a CO pressure of 1 MPa (initial pressure), as
2
1
13
confirmed by H and C NMR measurements (i.e., signals at
8.3 and 160 ppm, respectively). With excess CO2, both Si­H
bonds could be activated to yield (HCOO) SiPh with m/z =
1
to a J. Young NMR tube for analysis. H NMR (400 MHz): 8.3
ppm for HCOOSiR3; 13C{ H} NMR (100 MHz): 160 ppm for
1
2
2
HCOOSiR3.
272 (Figure S7, supporting information). In the presence of
phen and other zinc salts, such as ZnBr , ZnI , and Zn(ClO ) ,
0
(2) Bis(silyl)acetal (C ): Zn(OAc) (0.02 mmol, 3.7 mg),
2
2
2
4 2
phen (0.06 mmol, 10.8 mg), CD CN (1 mL), Ph SiH (2 mmol,
the catalytic reactivities were poor, while in the presence of
ZnCl , ZnSO , and Zn(OTf) (OTf = trifluoromethanesulfo-
3
2
2
3
68 mg) were added to an autoclave. The autoclave was sealed
2
4
2
tightly, and filled with CO to 0.25 MPa (initial pressure). After
nate), the reduction of CO to silyl formate was observed in
2
2
2
4 h reaction at room temperature, CO was released gently,
moderate to good yields. Polar solvent was good media while
non-polar solvent (e.g. toluene) was not preferred (Table 1). In
addition to Ph SiH , we found that PhSiH was also a good
2
and mesitylene was added as an internal standard. The solu-
tion was then transferred to a J. Young NMR tube for NMR
2
2
3
1
analysis. H NMR (400 MHz): 5.8 ppm for CH (OSiR );
source for CO hydrosilylation, however, Ph SiH, Et SiH, and
2
3
2
3
3
13
1
C{ H} NMR (100 MHz): 83 ppm for CH (OSiR ).
(EtO) SiH had poor reactivities (Table S1).
2
3
3
¹II
(
3) Methoxysilane (C ): Zn(OAc) (0.02 mmol, 3.7 mg),
We therefore considered that the catalyst efficiency was
determined by interactions between hydrosilane and the
counteranion of the zinc salt (i.e., an O or Cl donor). The
influence of the acetate anion on activation of the Si­H bond
2
phen (0.06 mmol, 10.8 mg), CD CN (1 mL), Ph SiH (3 mmol,
5
tightly, and filled with CO to 0.25 MPa (initial pressure). After
2
3
2
2
52 mg) were added to an autoclave. The autoclave was sealed
2
1
4 h reaction at 80 °C, CO2 was released gently, and mesitylene
was therefore monitored by H NMR spectroscopy. Thus, in the
was added as an internal standard. The solution was then trans-
1
ferred to a J. Young NMR tube for NMR analysis. H NMR
13
1
(
400 MHz): 3.6 ppm for CH OSiR ; C{ H} NMR (100 MHz):
3 3
5
2 ppm for CH OSiR .
3 3
1
3
¹IV
(
4) CH (C ): Zn(OAc) (0.01 mmol, 1.8 mg), phen
4
2
(
0.03 mmol, 5.4 mg), B(C F ) (0.01 mmol, 5.1 mg), C D (0.15
6 5 3 6 6
mL), Ph SiH (0.5 mmol, 92 mg) were added to a valved NMR
2
2
tube, and filled with 13CO2 to 0.25 MPa (initial pressure). Then
1
the NMR tube was heated to 80 °C for 24 h reaction. H NMR
1
3
(
¹
400 MHz): 0.16 ppm (d, J = 125 Hz). C NMR (100 MHz):
4.57 ppm (q, J = 125 Hz). 13C{ H} NMR (100 MHz): ¹4.57
1
ppm (s).
Scheme 2. H/D exchange and neutralization.
1946 | Bull. Chem. Soc. Jpn. 2019, 92, 1945–1949 | doi:10.1246/bcsj.20190203
© 2019 The Chemical Society of Japan

Table 1. Catalyst and solvent screening for CO2 hydro-
+II a
silylation to silyl formate (C ).
Entry
Catalyst
Yield
1
2
3
4
5
6
7
8
9
Zn(OAc)2/phen
ZnCl2/phen
ZnBr2/phen
99%
78%
trace
16%
95%
trace
53%
99%
7%
ZnI2/phen
ZnSO4/phen
Zn(ClO4)2/phen
Zn(OTf)2/phen
b
Figure 2. Eyring plot of CO2 hydrosilylation to C+II from
25 to 55 °C. Reaction conditions: Ph2SiH2 (0.1 mmol),
Zn(OAc)2 (0.002 mmol), phen (0.006 mmol), MeCN
Zn(OAc)2/phen
Zn(OAc)2/phen
none
c
10
trace
+II
aReaction conditions: Ph2SiH2 (1 mmol), Zn salt (0.02 mmol),
phen (0.06 mmol), CD3CN (1 mL), CO2 (1 MPa), 24 h, 25 °C.
Yields were determined by H NMR (400 MHz) using mesit-
ylene as the internal standard. Solvent = DMF. Solvent =
toluene.
(1 mL), CO2 (1 MPa), 15 min. Yield of C
by H NMR using mesitylene as the internal standard.
was determined
1
1
b
c
Table S3. We found that at 125 °C, the turnover number (TON)
reached 815000 (81.5% yield) with high thermostability and a
catalyst loading of 1 ppm. To the best of our knowledge, no
5
TON >10 has been reported for the catalytic CO hydro-
2
+
II
silylation to C . Other outstanding examples include a copper
N-heterocyclic carbene complex (TON = 7500), Ru (CO)
TON = 9000), and a copper diphosphine complex (TON =
0000).
Further reduction of CO with hydrosilane was found to yield
2
9
3
12
2
2
(
7
2
8
2
0
C . However, tuning the selectivity of this step was challenging,
as a precise 2:1 molar ratio of hydrosilane to CO must be
2
employed. Interestingly, in the presence of greater quantities of
+
II
CO , the formation of C was preferred, while with higher
2
¹
II
hydrosilane contents, methoxysilane C was formed prefer-
entially. The amount of CO2 in the autoclave was calculated
Figure 1. 1H NMR shifts (CD3CN, 400 MHz) of Ph2SiH2
and 1 mixture at 25 °C. Tetramethylsilane (TMS) was add-
ed as an internal standard (0.0000 ppm).
using the ideal gas equation. At 25 °C, 1 mmol CO was reduced
2
in the presence of 2 mmol Ph SiH and 1 in CD CN to give
2
2
3
0
0
.40 mmol bis(silyl)acetal C , as confirmed by the observation
of H and C{ H} NMR signals at 5.8 and 83 ppm, respec-
tively. In addition, the reduction of CO to C was disfavored
1
13
1
0
2
at high temperatures. More specifically, upon increasing the
¹II
temperature to 80 °C, the preferred product was C (methoxy-
silane, CH3OSiR3), which represents the same oxidation state
as methanol. Longer reaction times led to over-reduction and
¹
II
the formation of C (Figure S12, supporting information). The
¹
II
1
product C
was confirmed by the observation of H and
Scheme 3. Proposed interactions between the hydrosilane
and 1 (L = 1,10-phenanthroline).
1
3
1
C{ H} NMR signals at 3.6 and 52 ppm, respectively.
0
Unexpectedly, upon the attempted preparation of a C prod-
1
3
13
presence of 0.1 equiv. 1, the position of the Si­H signal of
Ph SiH was shifted upfield from 4.8887 to 4.8678 ppm. More-
uct from CO , the formation of CO was observed, which
2
was catalyzed by 1 in a valved NMR tube at 25 °C in CD CN
2
2
3
over, in the presence of 0.2 and 0.3 equiv. of 1, more significant
shifts to 4.8586 and 4.8461 ppm were observed (Figure 1). It
therefore appeared that a six-member ring was formed with the
(Figure 3) confirmed by the observation of a signal at 184 ppm
in the C NMR spectrum. Although catalytic reduction of CO2
to CO has been documented with electro- and photo-catalytic
1
3
7
interaction between Zn(OAc) and Si­H thereby activating the
processes, the characterization of CO from CO hydrosilyla-
2
2
7
3
Si­H bond for the subsequent CO insertion (Scheme 3). With
tion was challenging. However, upon attempting the prepa-
ration of silyl formate, only traces of CO were detected,
illustrating that no competing reaction existed between silyl
formate (C ) and CO. Nevertheless, it appeared that a com-
peting reaction existed between CO and bis(silyl)acetal (C )
2
1
3
Zn(ClO ) , there was almost no NMR shift. Eyring analysis
4
2
+
II
of CO hydrosilylation to C
resulted ¦H = 19.3 kJ mol , ¦S = ¹249 J mol K , and
G 298 = 93.5 kJ mol . The large negative entropy of activa-
from 25 to 55 °C (Figure 2)
2
‡
¹1
‡
¹1 ¹1
+II
‡
¹1
0
¦
0
tion is in agreement with an association mechanism.
due to the relatively low yield of C .
As the CO hydrosilylation could be carried out with de-
The full reduction of CO by hydrosilane resulted in the
2
2
creased loadings of 1, we moved on to examine the efficiency
production of CH . Theoretically, the reduction of CO to CH
4
(C ) requires at least 4 equiv. of hydrosilane. However, we
4
2
+II
¹IV
of 1 in the hydrosilylation of CO to C , as summarized in
2
Bull. Chem. Soc. Jpn. 2019, 92, 1945–1949 | doi:10.1246/bcsj.20190203
© 2019 The Chemical Society of Japan | 1947

information, except Ni(OAc) for CO hydrosilylation to C¹II).
2
2
These observations therefore removed the limitation of the
metal employed in the CO2 hydrosilylation process, with
metals from different periodic groups being suitable. However,
we did note that the selection of an appropriate counteranion
was necessary for this process.
4
. Conclusion
Figure 3. Confirmation of 13CO formation by 13C NMR
spectroscopy (100 MHz, CD3CN) at 25 °C. Reaction con-
In summary, we successfully employed Zn(OAc) /phen
catalyst (1) for the step-by-step hydrosilylation of CO to CH
4
through silyl formate (C ), bis(silyl)acetal (C ), methoxy-
silane (C ). With CO , the final reduction product CH4
was fully characterized by H, C{ H}, and 13C NMR, co-
2
1
3
2
ditions: 0.4 mmol Ph2SiH2, 0.2 mmol CO2, 2 mol% 1,
5 °C. (A) 10 min and (B) 2 h.
+II
0
2
¹II
13
13
2
1
13
1
catalyzed by B(C F ) . The reaction conditions and selectivity
6
5 3
were summarized in Table S7 and Table S8. Unusually, we
1
3
accomplished the catalytic CO2 hydrosilylation to yield
1
3
CO. In addition to zinc-based catalyst 1, other metal acetate
catalysts (M(OAc) , M = Mn, Fe, Co, Ni, or Cu) also served as
2
catalysts for the CO hydrosilylation. We therefore expect that
2
our described process can be applicable in the area of organic
and green synthesis for the transformation of amines (RR¤NH)
to N-formamides (RR¤N­CHO) and N-methylamines (RR¤N­
7
5­78
CH3) using CO2 as the C1 building block.
Studies are
currently ongoing in our laboratory into the above method.
We thank the New Energy and Industrial Technology Devel-
opment Organization (NEDO, Grant P16010) for supporting
this work.
1
3
Figure 4. Confirmation of CH4 formation in C6D6 at
1
13
Supporting Information
2
5 °C: (A) H NMR (400 MHz), (B) C NMR (100 MHz),
C) C{ H} NMR (100 MHz) after 5 h reaction, and (D)
C{ H} NMR (100 MHz) after 24 h reaction.
1
3
1
(
Detailed NMR spectra, silane screening, and the summary of
reaction conditions and selectivity. This material is available on
https://doi.org/10.1246/bcsj.20190203.
1
3
1
¹
II
found that CH formation was not observed at 80 °C, with C
4
being observed instead. Fortunately, the addition of tris(penta-
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Bull. Chem. Soc. Jpn. 2019, 92, 1945–1949 | doi:10.1246/bcsj.20190203
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