Catalytic reduction of CO2with organo-silanes using [Ru3(CO)12]

Article abstract of DOI:10.1016/j.jorganchem.2016.08.032

The reaction of carbon dioxide with Et₃SiH in the presence of catalytic amounts of [Ru₃(CO)₁₂] as a catalytic precursor was achieved to produce silyl formate (Et₃SiOCOH) 1s with a TON of 9000. A similar reaction in the presence of KF yielded potassium formate (8s) in a one-pot protocol with high selectivity using water or MeCN as the solvent. In the current report the complete reduction of carbon dioxide to methane was achieved, with the use of a more reactive silane (phenylsilane). A catalytically relevant species was the ruthenium cluster [H₄Ru₄(CO)₁₂]. This is the second report on the hydrosilylation of carbon dioxide catalyzed by highly active and readily available ruthenium clusters and this is the first report of hydrosilylation of CO₂to methane.

Full text of DOI:10.1016/j.jorganchem.2016.08.032

Accepted Manuscript
Catalytic reduction of CO with organo-silanes using [Ru (CO)
]
2
3
12
Tamara Jurado-Vázquez, Carmen Ortiz-Cervantes, Juventino J. García
PII:
S0022-328X(16)30373-4
10.1016/j.jorganchem.2016.08.032
JOM 19611
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 18 July 2016
Revised Date: 30 August 2016
Accepted Date: 31 August 2016
Please cite this article as: T. Jurado-Vázquez, C. Ortiz-Cervantes, J.J. García, Catalytic reduction of
CO with organo-silanes using [Ru (CO) ], Journal of Organometallic Chemistry (2016), doi: 10.1016/
2
3
12
j.jorganchem.2016.08.032.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Catalytic Reduction of CO2 with Organo-Silanes using
[Ru3(CO)12]
Tamara Jurado-Vázquez, Carmen Ortiz-Cervantes and Juventino J García.
Facultad de Quimica. Universidad Nacional Autonoma de México. Mexico City 04510.
Mexico.

ACCEPTED MANUSCRIPT
Catalytic Reduction of CO2 with Organo-Silanes using
[Ru3(CO)12]
Tamara Jurado-Vázquez, Carmen Ortiz-Cervantes and Juventino J García*
Facultad de Quimica. Universidad Nacional Autonoma de Mexico. Mexico City 04510.
Mexico.
Abstract
The reaction of carbon dioxide with Et3SiH in the presence of catalytic amounts of
[Ru3(CO)12] as a catalytic precursor was achieved to produce silyl formate (Et3SiOCOH) 1s
with a TON of 9 000. A similar reaction in the presence of KF yielded potassium formate
(8s) in a one-pot protocol with high selectivity using water or MeCN as the solvent. In the
current report the complete reduction of carbon dioxide to methane was achieved, with the
use of a more reactive silane (phenylsilane). A catalytically relevant species was the
ruthenium cluster [H4Ru4(CO)12]. This is the second report on the hydrosilylation of carbon
dioxide catalyzed by highly active and readily available ruthenium clusters and this is the
first report of hydrosilylation of CO2 to methane.
Key words: carbon dioxide; reduction; silane; formate; ruthenium; catalysis.
1

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Introduction
The increasing abundance of carbon dioxide in the atmosphere is currently one of the topics
of great interest. Particularly, the use of this contaminant gas as a C1 source represents a
challenge in the efficient production of high value-added materials and fuels.1 CO2 is a
molecule with high thermodynamic stability and consequently low reactivity. Therefore,
the use of catalytic methods is an attractive option for the activation of this gas.
Among all possible transformations of CO2 to C1 or higher chemicals, the most attractive
and promising reactions in terms of energy balance, catalyst performance, reusability, and
scale-up perspective are hydrogenation to formate, methanol, or methane, reduction to CO
and production of (poly)carbonate (Figure 1).2
HCOOH
H3COH
H2
CH4
RNH2
HCONHR
e- , H+
CO2
CO
O
O
O
n
O
Figure 1. Possible transformations of CO2
The hydrogenation methods are of particular interest since the corresponding products are
more reactive than carbon dioxide and can be used as raw materials for the preparation of a
2

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wide variety of organic products or fuels. However, even when H2 is highly reactive, it also
represents a problem in terms of safe handling. Thus, the use of alternative hydrogenation
procedures for carbon dioxide that replace H2 with safer hydrogen sources such as organo-
silanes are desirable.
The hydrogenation of carbon dioxide to methane with silanes involves four steps. Silyl
formate is the product of the first step, and two molecules of disiloxane are produced along
with methane for the final step.3,4 An important consideration for carbon dioxide
hydrogenation using silanes is that the Si-H bond is relatively easy to activate. In the
presence of a metal-containing catalyst, it produces an active hydride, ultimately yielding
the formation of strong Si-O bonds. Based on our experience in carbon dioxide
hydrosilylation using nickel catalysts,5,6 we decided to expand this chemistry to the use of
ruthenium catalytic precursors, particularly ruthenium clusters. In the literature there are
reports of hydrosilylation of carbon dioxide with other metals such as Ir, Pt, Pd, Zr and Cu
with high activity.7–11
We found that the use of simple ruthenium clusters in the hydrosilylation of CO2 remains as
a relatively un-explored area. There are many theoretical studies regarding carbon dioxide
hydrogenation with metal clusters,12–15 as well as experimental reports about carbon dioxide
reduction with metal clusters.16–26 some reports specifically deal with carbon dioxide
hydrogenation using the ruthenium cluster [Ru3(CO)12] and H2(g),
20,22 and just one report
employed hydrosilylation.27 Since the hydrosilylation protocols are safer and practical
alternatives for hydrogenation, we present our findings on the hydrosilylation of carbon
dioxide with a simple ruthenium cluster, which is 30 times more active than previously
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reported,27 and the first report of complete reduction to methane with silanes using
ruthenium.
Results and discussion
The catalytic hydrogenation of carbon dioxide with Et3SiH using [Ru3(CO)12] as a catalytic
precursor was achieved. First, the reaction times of 1, 25, and 48 h were assessed, and the
best conversion was achieved at 48 hours. The reaction was conducted using a 1 % load of
[Ru3(CO)12] relative to Et3SiH. The reaction occurred at 80 °C in 1 atm of CO2 and was
monitored by GC-MS. The main hydrogenation product from CO2 was the silyl formate
(1s), which is a relevant product that can be used as a starting material for a wide variety of
important products for industry and academia (Figure 2).
Figure 2. Some silyl formate applications
The polarity of different solvents such as MeCN, toluene, and MeOH was also assessed
(Table 1). The only solvent where carbon dioxide was actually reduced was acetonitrile,
with a 15 % conversion to 1s (Entry 3). Clearly, the use of low-polarity solvents such as
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toluene does not allow the reaction, and the use of methanol produced the silane solvolysis
to yield 5s.
According to our previous results with nickel catalysts,5 an important feature of this
transformation is the strong dependence on the use of Et3B as an additive to enhance the
hydrogenation of carbon dioxide. Therefore, we initially used Et3B, but in order to
determine the actual need for this additive in the current reduction of CO2, the reaction was
also performed without Et3B (Table 2, entry 2). To our surprise, the absence of this
additive in the current case improved the conversion of 1s, so we did not use it further.
Table 1. Reaction of CO2 and Et3SiH using [Ru3(CO)12]a,b,c
Conversion (%)
Entry
Solvent
1s
2s
3s
4s
5s
total
MeOH
Toluene
MeCN
nd
6
nd
nd
93
99
1
2
3
nd
15
nd
55
nd
5
nd
14
nd
nd
0
89
a) nd: not detected, b) All yields were determined by GC-MS, using Et3SiOCOH as internal std, c)
Reaction conditions: Et3SiH (1.55 mmol), [Ru] (0.0155 mmol), Et3B (0.155 mmol), CO2 (1
atm), solvent (5 mL). 80 °C, 48 h.
5

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Table 2. The influence of Et3B in CO2 hydrogenationa,b,c
Conversion (%)
Entry
Et3B
1s
15
29
2s
55
10
3s
5
4s
14
10
Total
89
10 mol%
--
1
2
nd
45
a) nd: not detected, b) All yields were determined by GC-MS, using Et3SiOCOH as internal std, c)
Reaction conditions: Et3SiH (1.55 mmol), [Ru] (0.0155 mmol), Et3B (0.155 mmol), CO2 (1
atm), solvent (5 mL). 80°C, 48 h.
We next carried out an assessment for a variety of mild temperatures and CO2 pressure in
order to obtain a higher conversion of carbon dioxide reduction to 1s. Key results are
presented in Table 3. The best conversion and selectivity to product 1s takes place in 100
psi of carbon dioxide and at 80 °C (entry 2). Considering that [Ru3(CO)12] is a well-known
precursor of nanoparticles,28–41 a mercury drop test was conducted to assess the
homogeneity of the process (entry 8).42, 35 As a result, no significant decrease in activity
was observed, meaning this reaction is likely to be a homogeneous process.
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Table 3. Testing at different temperatures and pressuresa,b,c
Conditions
Conversion (%)
Entry
Pressure
Temperature
(°C)
1s
2s
4s
total
(psi)
500
100
50
80
80
47
87
60
12
69
56
74
80
16
9
30
3
93
99
92
22
97
87
98
97
1
2
80
17
8
15
2
3
100
200
500
500
100
60
4
100
80
22
18
18
8
6
5
13
6
6
100
80
7
8a)
9
a) Hg drop test (0.309 mmol), b) all yields were determined by GC-MS, using Et3SiOCOH as
internal std, c) Reaction conditions: Et3SiH (3.1 mmol), [Ru] (0.031 mmol), MeCN (10 mL).
To investigate the catalyst load, the reaction was initially carried out with 1 mol % load of
[Ru3(CO)12], which was successfully reduced to 0.01 mol % with a TON of 9 000 (see
Supporting Information). This ruthenium cluster was compared with other mononuclear
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and dinuclear ruthenium catalytic precursors (see Table 4), and the use of [Ru3(CO)12]
represents the most active one reported for the hydrosilylation of CO2.
Table 4. Reported catalysis of ruthenium for hydrosilylation of CO2
Conditions
Precatalyst
Silane
TON
T (°C) / P (psi) / T(h) / solv
80 / 100/ 48 /MeCN
Et3SiH
9 000
485
91
[Ru3(CO)12]*
[RuCl3(MeCN)3]43
[RuCl3·nH2O]44
[Ru2Cl5(MeCN)7]45
[RuH2(PMe3)4]46
[RuCl2(PPh3)3]47
Me2PhSiH
Me2PhSiH
Me2PhSiH
MeEt2SiH
MeEt2SiH
85 / 293/ 1½ /MeCN
80 / 1028/ 20 / MeCN
80 / 205 / 20 / MeCN
90 / 2939 / 63 /scCO2
100 / 440 / 20 / benzene
970
62
14
48
Et3SiH
Et3SiH
80 / 73 / 4 / benzene
50
[((Ph3P)2N)][HRu3(CO)11]27
100 / 734 / 24 /CH2Cl2
292
*This work.
To identify some of the involved active species in the catalytic process, a reaction of Et3SiH
was carried out with [Ru3(CO)12] following a reported procedure (Scheme 1).49 However,
we used acetonitrile instead of toluene, and the 1H NMR spectrum of the crude reaction
displayed three signals between -17 and -18.5 ppm. After purification by column
8

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chromatography, only one hydride was recovered, which showed a signal at -17.8 ppm.
This compound has been previously characterized as [H4Ru4(CO)12].50 This is an air-stable
cluster that can be handled in the open atmosphere.
MeCN, 4 h
4Et3SiH + [Ru3(CO)12]
[H4Ru4(CO)12]
80 °C
Scheme 1.
To find out if the cluster [H4Ru4(CO)12] was a catalytically relevant species, it was
independently synthetized51 and used. A comparison of its catalytic activity with that of
[Ru3(CO)12] is presented in Table 5.
Table 5. Catalytic activity using both ruthenium clustersa,b
Conversion (%)
Cluster
1s
49
47
2s
32
29
6s
15
21
Total
96
[Ru3(CO)12]
[H4Ru4(CO)12]
97
a) all yields were determined by GC-MS, using Et3SiOCOH as internal std, b) Reaction conditions:
Et3SiH (3.1 mmol), [Ru] (0.0046 mmol), MeCN (10 mL).
9

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As shown in the table, both ruthenium clusters presented practically the same catalytic
activity. Consequently, we established that [Ru4(H)4(CO)12] was produced in situ and able
to work as catalytic precursor. The silyl formate (1s) is a product of great industrial interest
(Figure 2). However, some practical disadvantages are associated with it, such as
complicated handling and tendency to be readily hydrolyzed. A practical alternative to
overcome these inconveniences is the production of potassium formate by reacting the silyl
formate with KF (Figure 2). Thus, to obtain potassium formate using a one-pot procedure,
a similar reaction for the CO2 reduction was conducted but with KF added from the
beginning the reaction to yield potassium formate in a 75 % conversion (Table 6).
Noteworthy, the ruthenium-free control reactions revealed no reaction at all.
10

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Table 6. Potassium formate obtained in one-pot procedurea,b
Conversion (%)
Entry
time (h)
2s
24
26
20
23
8s
75
73
74
67
total
99
48
24
13
5
1
2
3
4
99
94
90
a) all yields were determined by GC-MS, using Et3SiOCOH as internal std, b) Reaction conditions:
Et3SiH (3.1 mmol), KF (3.1 mmol), [Ru] (0.00155 mmol), MeCN (10 mL).
The product Et3SiF (7s) thermodynamically directs the reaction due to the formation of a
strong Si-F bond. This allowed for shorter reaction times to be considered (entries 2-4,
Table 6), and the reaction time was decreased from 48 to 5 hours with good conversion to
potassium formate (8s). To make this a green process, the reaction was tested in water as a
solvent instead of MeCN, through which 8s was successfully produced in 60% yield
(Scheme 2).
11

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Scheme 2.
Using similar reaction conditions to those in in Table 2 but with PhSiH3 instead of Et3SiH
and the optimized catalyst load (0.05 mol%), the reaction was conducted and monitored by
NMR and CG/MS. This reaction is presented in Scheme 3, for which a more active silane
was used to obtain a complete reduction of CO2 to methane. The product was characterized
by 1H and 13C{1H} NMR, including the use of isotopically labeled carbon dioxide (13CO2).
The final gas mixture dissolved in C6D6 contained approximately 28% CH4 (see Supporting
Information section, Figure S6).
Scheme 3.
CONCLUSIONS
The hydrosilylation of carbon dioxide was achieved by using [Ru3(CO)12] and
[H4Ru4(CO)12] as catalysts precursors. This is the second report on this topic and the first
report for the complete reduction of CO2 to methane using ruthenium and phenylsilane
under relatively mild conditions. Also, it was possible to produce silyl formate with good
yield and selectivity. Additionally, potassium formate was produced in water with good
yield.
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EXPERIMENTAL SECTION
General considerations. Unless otherwise stated, all processes were performed using an
MBraun glovebox (<1 ppm H2O and O2) under an argon atmosphere (Praxair 99.998) or by
using high-vacuum and standard Schlenk techniques under an argon atmosphere.
Acetonitrile was dried and distilled over CaH2, toluene was dried and distilled over sodium,
methanol was dried and distilled from a solution of magnesium/iodine, and water was
distilled and deoxygenated under an argon flow. Deuterated solvents for NMR experiments
were purchased from Cambridge Isotope Laboratories. Triethylsilane (99% purity,
Aldrich), carbon dioxide (99.998% purity, supplied by Praxair), phenylsilane (97% purity,
Aldrich), triethylborane (95% purity, Aldrich), and triruthenium dodecacarbonyl (99%
Aldrich) were used. All reagents for the catalytic reactions were loaded in the glove box.
The GC-MS determinations were made using an Agilent 5975C system equipped with a 30-
m DB-5MS capillary column (0.25 mm i.d.; 0.25 µm).
Reaction monitoring. The reaction was performed using a 50-mL Schlenk flask equipped
with a Rotaflo valve and a magnetic stirring bar. It was loaded with 9.8 mg (0.015 mmol) of
[Ru3(CO)12], 180 mg (1.53 mmol) of Et3SiH, 15.8 mg (0.153 mmol) of Et3B, 5 mL of
MeCN, and CO2 atmosphere. All reagents were loaded in a glove box except CO2, which
was added using a double manifold gas/vacuum. The mixture was heated at 80 °C in a
silicon oil bath for 1 h, and the reaction was then depressurized in a hood, opened under
argon atmosphere, and analyzed by GC/MS. For further reaction time, the reaction mixture
was pressurized again with CO2 and heated at 80 °C. A sample was taken after 24 h and
then after a total of 48 h.
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Reactivity of CO2 with Et3SiH catalyzed by [Ru3(CO)12] in different solvents. The
reaction was performed in a 50-mL Schlenk flask equipped with a Rotaflo valve and a
magnetic stirring bar. The flask was loaded with 9.8 mg (0.015 mmol) of [Ru3(CO)12], 180
mg (1.53 mmol) of Et3SiH, 15.8 mg (0.153 mmol) of Et3B, and 5 mL of MeCN, and then
pressurized with CO2. All the reagents were loaded in a glove box except CO2, which was
added using a gas/vacuum double manifold. The mixture was heated at 80 °C in a silicon
oil bath for 48 h. This methodology was also done using toluene and MeOH instead of
MeCN.
Use of different CO2 pressures. The pressures were examined in a 100-mL stainless steel
Parr autoclave, and the reactor was loaded with 19.6 mg (0.030 mmol) of [Ru3(CO)12], 360
mg (3.06 mmol) of Et3SiH, 10 mL of MeCN, and CO2 at a desired pressure. Then, the
reactor was heated at different temperatures for 48 h. After this time, the reactor was cooled
to room temperature and depressurized in a hood. The final reaction mixture was analyzed
by GC/MS.
Hg drop test. This reaction was performed as described for the previous reaction, but with
the addition of 61.0 mg (0.306 mmol) of Hg and CO2 at 100 psi followed by heating at 80
°C for 48 h. The reaction mixture was filtered on celite and analyzed by GC/MS.
Load of [Ru3(CO)12]. All reactions were performed in a 100-mL stainless steel Parr
autoclave. The reactor was loaded with 360 mg (3.06 mmol) of Et3SiH, 10 mL of MeCN,
100 psi of CO2 , and 10.7 mg, 1.6 mg, or 1.0 mg (0.0167 mmol, 2.5x103 mmol, 1.6x10-3
mmol respectively) of [Ru3(CO)12]. These amounts represent catalyst loads of 0.54, 0.08,
and 0.05 mol %, respectively. Particularly for the reaction using 0.01 mol % catalyst, the
14

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reaction was carried out with 1.0 mg (1.6x10-3 mmol) of [Ru3(CO)12], 1815 mg (15.64
mmol) of Et3SiH, 10 mL of MeCN, and 100 psi of CO2. All reactions were heated at 80 °C
for 48 h, and the reaction mixtures where analyzed by GC/MS.
Identification of catalytic species. This reaction was carried out in a 50-mL Schlenk flask
equipped with a Rotaflo valve and a magnetic stirring bar. The flask was loaded with 50.0
mg (0.078 mmol) of [Ru3(CO)12], 39.3 mg (0.338 mmol) of Et3SiH, and 5 mL of MeCN,
and the reaction was heated at 80 °C for 4 h. Then, the reaction was evaporated to dryness
and purified by column chromatography in a glove box and carried out using silica and a
mixture of THF/acetone as eluent. The product was identified as [H4Ru4(CO)12]50 by a
characteristic 1H NMR peak at -17.8 ppm (22°C, 300 MHz, THF-d8).
One-pot synthesis of potassium formate. The reaction was carried out in a 100-mL
stainless steel Parr autoclave. The reactor was loaded with [Ru3(CO)12] (1.0 mg 1.6x10-3
mmol), Et3SiH (360 mg 3.06 mmol), KF (179.8 mg, 3.06 mmol), 10 mL of MeCN or water,
and CO2 (100 psi), and heated at 80 °C for 13 h. When MeCN was used as the solvent, the
final mixture was filtered over celite and analyzed by GC/MS, but when the reaction was
performed in water, it was analyzed by 1H NMR (22 °C, 300 MHz, D2O) 8.40 ppm
(KOC(O)-H). Isolated yield = 60%
CO2 reduction with phenylsilane. A 100-mL stainless steel Parr autoclave was loaded
with [Ru3(CO)12] (1.0 mg 1.6x10-3 mmol), PhSiH3 (338.0 mg 3.06 mmol), Et3B (61.2 mg,
0.31 mmol), 10 mL of MeCN, and CO2 (100psi), and heated at 80°C for 48 h. Then, the
reactor was cooled and depressurized while bubbling the gas into a Benzene-d6. The
reaction residue was analyzed by GC/MS, and gases were analyzed by 1H and
15

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13C{1H}NMR in an NMR tube with a J. Young valve. 1H NMR (22 °C, 300 MHz,
Benzene-d6): δ 0.52 ppm (CH4). 13C{1H}NMR (22 °C, 300 MHz, Benzene-d6): δ 0.11 ppm
(CH4).
A similar experiment was made using 13CO2.
Supporting Information available.
Relevant experimental data, NMR spectra and GC-MS determinations.
AUTHOR INFORMATION
Corresponding Author
E-mail: juvent@unam.mx
Acknowledgements
We thank CONACYT (178265), DGAPA-UNAM (IN-202516) and PAIP-FQ for their
financial support. We also thank Dr. Alma Arévalo for technical support.
REFERENCES
(1)
(2)
Aresta, M. Carbon Dioxide as Chemical Feedstock; (2010).
Anthofer, M. H.; Wilhelm, M. E.; Cokoja, M.; Ku, F. E. Transformation and
16

ACCEPTED MANUSCRIPT
Utilization of Carbon Dioxide; (2014).
(3)
(4)
(5)
S. N. Riduan, J. Y. Ying, Y. Zhang, ChemCatChem 5 (2013) 1490–1496.
M. Khandelwal, R. J. Wehmschulte, AngewChem 51(2012) 7323–7326.
L. Gonzalez-Sebestian, M. Flores-Alamo, J. J. Garcia, Organometallics 32 (2013)
7186–7194.
(6)
L. González-Sebastián, M. Flores-Alamo, J. J. García, Organometallics 34 (2015)
763–769.
(7)
(8)
(9)
T. C. Eisenschmid, R. Eisenberg, Organometallics 8 (1989) 1822–1824.
T. Matsuo, H. Kawaguchi, J. Am. Chem. Soc. 128 (2006) 12362–12363.
S. J. Mitton, L. Turculet, Chem. - A Eur. J. 18(2012) 15258–15262.
(10) K. Motokura, D. Kashiwame, A. Miyaji, T. Baba Org. Lett. 14 (2012) 2642-2645.
(11) S. Park, D. Be, M. Brookhart, J. Am. Chem. Soc. 134 (2012) 11404-11407.
(12) S. Gautam, N. Goel, K. Dharmvir, AIP Conf. Proc. 1591 (2014) 364-365.
(13) L. Ma, M. Melander, K. Laasonen J. Akola, Phys. Chem. Chem. Phys. 17 (2015),
7067–7076.
(14) S. Gautam, K. Dharamvir N. Goel, Comput. Theor. Chem. 1009 (2013) 8–16.
(15) H. Tominaga and M. Nagai, Appl. Catal. A Gen. 282 (2005) 5–13.
(16) J. Li, P. González-Navarrete, M. Schlangen and H. Schwarz, Chem. Eur. J. 21
17

ACCEPTED MANUSCRIPT
(2015) 7780–7789.
(17) D. M. Ermert, I. Ghiviriga, V. J. Catalano, J. Shearer and L. J. Murray, Angew.
Chemie Int. Ed. 54 (2015) 7047-7050.
(18) A. Taheri, E. J. Thompson, J. C. Fettinger and L. A. Berben, ACS Catal. 5 (2015)
7140-7151.
(19) F. Calaza, C. Stiehler, Y. Fujimori, M. Sterrer, S. Beeg, M. Ruiz-Oses, N. Nilius, M.
Heyde, T. Parviainen, K. Honkala, H. Häkkinen and H.-J. Freund, Angew. Chem.
Int. Ed. 54 (2015) 12484-12487.
(20) D. J. Darensbourg and C. Ovalles, Inorg. Chem. 25 (1986) 1603–1609.
(21) K. Tanaka, Y. Kushi, K. Tsuge, K. Toyohara, T. Nishioka and K. Isobe, Inorg.
Chem. 37 (1998) 120–126.
(22) S. D. Jackson, R. B. Moyes, P. B. Wells and R. J. Whyman, J.Chem. Soc., Faraday
Trans. 83 (1987) 905–911.
(23) D.-S. Park, M. A. Jabbar, H. Park, H. M. Lee, S.-C. Shin and Y.-B. Shim, Bull.
Korean Chem. Soc. 28 (2007) 1996–2002.
(24) S. M. Pillai, R. Ohnishi and M. Ichikawa, React. Kinet. Catal. Lett. 48 (1992) 201-
208.
(25) D. J. Darensbourg, C. Ovalles and M. Pala, J. Am. Chem. Soc. 105 (1983) 5937–
5939.
(26) J. Fesseler, J.-H. Jeoung and H. Dobbek, Angew. Chemie Int. Ed. 54 (2015) 8560-
18

ACCEPTED MANUSCRIPT
8564.
(27) G. Süss-Fink and J. Reiner, J. Organomet. Chem. 221 (1981) C36–C38.
(28) K. Aramaki, S. Kawaguchi, M. Saito, J. Kuwano and Y. Saito, Key Eng. Mater. 388
(2009) 65–68.
(29) C. Delacôte, A. Lewera, M. Pisarek, P. J. Kulesza, P. Zelenay and N. Alonso-Vante,
Electrochim. Acta.55 (2010) 7575–7580.
(30) S. Durón, R. Rivera-Noriega, P. Nkeng, G. Poillerat and O. Solorza-Feria, J.
Electroanal. Chem. 566 (2004) 281–289.
(31) S. Fiechter, I. Dorbandt, P. Bogdanoff, G. Zehl, H. Schulenburg and H. Tributsch, J.
Phys. Chem.111 (2007) 477–487.
(32) J. Krämer, E. Redel, R. Thomann and C. Janiak, Organometallics 27 (2008) 1976-
1978.
(33) Y. Motoyama, M. Takasaki, K. Higashi, S.-H. Yoon, I. Mochida and H. Nagashima,
Chem. Lett. 35 (2006) 876–877.
(34) C. Ortiz-Cervantes and J. J. García, Inorganica Chim. Acta. 397 (2013) 124–128.
(35) C. Ortiz-Cervantes, I. Iyañez, and J. J. García, J. Phys. Org. Chem. 25 (2012) 902–
907.
(36) M. Oubenali, G. Vanucci, B. Machado, M. Kacimi, M. Ziyad, J. Faria, A. Raspolli-
Galetti and P. Serp, ChemSusChem. 4 (2011) 950–956.
(37) Z. Song, T. Cai, J. C. Hanson, J. A. Rodriguez and J. Hrbek, J. Am. Chem. Soc. 126
19

ACCEPTED MANUSCRIPT
(2004) 8576–8584.
(38) M. Takasaki, Y. Motoyama, K. Higashi, S.-H. Yoon, I. Mochida and H. Nagashima,
Chem. Asian J. 2 (2007) 1524–1533.
(39) Y. Yu, S. Liu and J. Zhang, Diam. Relat. Mater. 19 (2010) 661–664.
(40) G. Zehl, P. Bogdanoff, I. Dorbandt, S. Fiechter, K. Wippermann and C. Hartnig, J.
Appl. Electrochem. 37 (2007) 1475–1484.
(41) C. Zhang, K. Yanagisawa, H. Tao, A. Onda, T. Shou and S. Kamiya, Catal. Letters
141 (2011) 1311–1315.
(42) R. H. Crabtree, Chem. Rev. 112 (2012) 1536–1554.
(43) P. Deglmann, E. Ember, P. Hofmann, S. Pitter and O. Walter, Chem. Eur. J. 13
(2007) 2864–2879.
(44) J A. Jansen, H. Görls and S. Pitter, Organometallics 19 (2000) 135–138.
(45) A. Jansen and S. Pitter, J. Mol. Catal. A Chem. 217 (2004) 41–45.
(46) P. G. Jessop, Top. Catal. 5 (1998) 95–103.
(47) H. Koinuma, F. Kawakami, H. Kato and H. Hirai, J. Chem. Soc., Chem. Commun.,
1981, 213–214.
(48) T. T. Metsänen and M. Oestreich, Organometallics 34 (2015) 543–546.
(49) C. K. Toh, H. T. Poh, C. S. Lim and W. Y. Fan, J. Organomet. Chem. 717 (2012) 9-
13.
20

ACCEPTED MANUSCRIPT
(50) S. Aime, R. Gobetto, A. Orlandi, C. J. Groombridge, G. E. Hawkes, M. D. Mantle
and K. D. Sales, Organometallics 13 (1994) 2375–2379.
(51) P. J. Dyson and J. S. Mclndoe, in Transition Metal Carbonyl Cluster Chemistry,
Gordon and Breach Science Publishers, 2000.
21

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Highlights
Catalytic Reduction of CO2 with Organo-Silanes using
[Ru3(CO)12]
Tamara Jurado-Vázquez, Carmen Ortiz-Cervantes and Juventino J García.
Facultad de Quimica. Universidad Nacional Autonoma de México. Mexico City 04510.
Mexico.
ꢀ Commercially available catalyst precursor and silanes
ꢀ Safe use of silanes as hydrogen sources
ꢀ Selective hydrogenation depending on the selected silane
ꢀ First report on the complete reduction of CO2 to methane with silanes and
ruthenium