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Research Article

Received: 2 March 2012, Revised: 9 April 2012, Accepted: 16 April 2012, Published online in Wiley Online Library: 2012

( DOI: 10.1002/poc.2962

Facile preparation of ruthenium nanoparticles with activity in hydrogenation of aliphatic and aromatic nitriles to amines
Carmen Ortiz-Cervantesa, Iliana Iyaeza and Juventino J. Garcaa*
The thermal decomposition of [Ru3(CO)12] allowed the production of ruthenium nanoparticles (NPs) with a unique activity for this metal in the hydrogenation of aliphatic nitriles, yielding the corresponding tertiary amines (selectivity >80%) and aromatic nitriles to secondary amines and imines at 140  C, employing a moderate hydrogen pressure. The use of several stabilizing agents such as sodium dodecylsulfate and sodium 2-ethylhexanoate allowed the stabilization of ruthenium NPs (Ru-NPs), and further reactivity in the hydrogenation process was assessed. The Ru-NPs were characterized by transmission electron microscopy and exhibited an average size of 23 nm. Copyright 2012 John Wiley & Sons, Ltd. Supporting information may be found in the online version of this paper. Keywords: nitriles; ruthenium nanoparticles; hydrogenation; amines; imines

The catalytic hydrogenation of nitriles has long been used for the preparation of various amines.[1] Typically, it is performed over metallic catalysts, mainly in homogeneous liquid phase.[2] This method is of high industrial relevance and has been applied to the commercial production of amines like hexamethylenediamine, derived from the hydrogenation of adiponitrile (ADN).[3] Lower alkylamines ranging from 2 to 5 carbon atoms have been used as solvents or reagents in pharmaceutical, agricultural and catalytic applications.[4] The catalytic hydrogenation of nitriles is a good atom economy example and a valuable route to production of amines.[5] In industry, simple alkyl and aryl nitriles are hydrogenated in the presence of heterogeneous catalysts such as Raney-type nickel and cobalt.[6,7] In a recent report, the complex HInCl2 was used in the reduction of aromatic and aliphatic nitriles to primary amines.[8] A conventional hydrogenation process leads to a mixture of products that regularly contain secondary and tertiary amines, due to the high reactivity of partially hydrogenated reaction intermediates, i.e. imines or Schiff bases.[9] The employed metal in the catalyst is one of the most important factors in determining the activity and selectivity for the hydrogenation of alkyl- or aryl-nitriles; particularly, the ruthenium-based catalysts[1012] largely exhibit the highest selectivity to primary amines, while palladium and platinum-based catalysts preferentially yield secondary and tertiary amines.[3,1315] The use of transition metal nanoparticles (NPs) in catalysis has gained interest since they mimic metal surface activation and heterogeneous catalysis at the nanoscale, showing, in several cases, higher selectivity and efciency compared to other heterogeneous catalysts. NPs can be envisaged as clusters containing from a few tens to several thousand metal atoms, usually stabilized by ligands, surfactants or polymers protecting their surfaces.[16] As catalysts, these systems can show a great

activity due to the potential large surface and their availability to chemically transform substrates.[17] Ru-NPs can be efciently obtained from [Ru3(CO)12] by thermal or photolytic decomposition under argon atmosphere.[1822] Interestingly, Ru-NPs can also be prepared and stabilized with nitrile-functionalized ionic liquids showing activity towards the hydrogenation of other nitrile-substituted aromatic compounds.[23] The use of metal NPs for nitrile hydrogenation has also been documented for silver NPs. In this case, acetonitrile (AN) was hydrogenated to yield the corresponding tertiary amine (triethylamine) along with NH3.[24] The use of bimetallic Ni-Ru catalyst supported on mesoporous silica has been assessed in the hydrogenation of AN. Conversion values depend on the Ni/(Ni + Ru) composition of the bimetallic catalysts. The Ru-rich bimetallic catalysts exhibited higher reactivity towards AN hydrogenation to yield ethylamine compared with pure Ni.[25] For several years, our group has been interested in the use of metal NPs in applications to catalysis. In a recent report, palladium NPs were successfully used in the desulfurization of dibenzothiophene via cross coupling reactions with Grignard reagents.[26] Herein, we report our ndings on the Ru-NPscatalyzed nitrile hydrogenation of alkyl and aryl nitriles.

All manipulations were performed using a MBraun glovebox (<1 ppm, H2O and O2). 100 mL and 300 mL stainless steel ParrW autoclaves were
* Correspondence to: J. J. Garca, Facultad de Qumica, Universidad Nacional Autnoma de Mxico, Mxico City 04510, Mxico. E-mail: a C. Ortiz-Cervantes, I. Iyaez, J. J. Garca Facultad de Qumica, Universidad Nacional Autnoma de Mxico, Mxico City 04510, Mxico

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used for the catalysis experiments. Benzonitrile (BN) and ADN were purchased from Aldrich in reagent grade. Propionitrile (J.T. Baker) was degassed using the freeze-pump-thaw method prior to its use. Tetrahydrofurane (J.T. Baker) was dried and distilled from dark purple solutions of sodium/benzophenone ketyl. AN reagent grade was purchased from J. T. Baker and was dried and distilled from calcium hydride prior to its use. Stabilizers polyvinylpyrrolidone (K value 2932), 2-ethylhexanoate, hexadecylamine and sodium dodecylsulfate were purchased from Aldrich. Ultra high purity hydrogen (5.0 from Praxair) was employed. Both the conversion and the selectivity of the catalytic reactions were determined via gas chromatographic analyses performed on an Agilent 5975 C equipped with a 30 m DB-5MS capillary (0.32 mm ID) column, following the decrease on the starting material peak. Infrared spectra were obtained using a Perkin-Elmer 1600 FT spectrophotometer. NMR spectra were acquired at room temperature using a 300 MHz Varian Unity Inova spectrometer. Transmission electron microscopy (TEM) micrographs were determined on a Jeol-2010 microscope equipped with a lanthanum hexaboride lament operating at an accelerating voltage of 200 kV. Samples for TEM observations were prepared by placing a thin lm of the heptanes Ru-NPs solution in a holey carbon grid. The metal particle size distribution was estimated from the measurement of about 200 particles, assuming a spherical shape, found in an arbitrary chosen area in enlarged micrographs.

Scheme 1. Stabilizers used for the catalytic hydrogenation reactions employing Ru-NPs, (1) polyvinylpyrrolidone (PVP), (2) sodium dodecylsulfate (SDS), (3) sodium 2-ethylhexanoate (SEH) and (4) hexadecylamine (HDA)

In-situ Ru-NPs preparation and AN hydrogenation experiments

A typical experiment was made as follows: [Ru3(CO)12] (10 mg, 0.0156 mmol) with 4 equiv of sodium dodecylsulfate and 20 mL of AN (379 mmol) were added to a batch reactor under inert atmosphere. The reactor was connected to a hydrogen gas reservoir and pressurized with 350 psi of H2 gas, then it was further heated up to 140  C, and the pressure drop was monitored. All suspensions produced at the end of the hydrogenation experiments were centrifuged (10 min at 5000 cycles/min) in order to recover the corresponding ruthenium NPs and further analyzed by TEM.

Figure 1. Hydrogenation of AN with Ru-NPs (0.004% mol) with 4 equiv of SDS at 140  C with 350 psi of hydrogen pressure for 3 days, ethylamine (EA), diethylamine (DEA) and triethylamine (TEA)

Benzonitrile (BN) hydrogenation experiments

Similarly as above described, the hydrogenation of BN with Ru-NPs was carried out on using the catalytic precursor [Ru3(CO)12] (5 mg, 0.008 mmol) loaded into a stainless steel autoclave along with BN (25 mL, 242.62 mmol) and SDS (5 equiv) in THF (25 mL). Then, the reaction mixture was pressurized up to 900 psi of hydrogen and further heated to 260  C for 24 h.

Figure 2. TEM images of ruthenium nanoparticles after the hydrogenation process: (A) in the absence of a stabilizing agent. (B) Nanoparticles formed in the presence of SEH and (C) Nanoparticles formed with SDS as stabilizers

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Typically were performed following the above-described procedures, while in addition to the reactants, two mercury drops were added into the reaction mixture. After completion, the solution was ltered and analyzed by GC-MS.


The Ru-NPs were obtained in situ by thermal decomposition of [Ru3(CO)12] under H2 and stabilized with a surfactant (vide infra), in addition, the IR spectra in solution did not show bands for any remaining metallic carbonyl, albeit the solutions were yellowbrown colored. The use of stabilizers allows diameter control of Ru-NPs, avoiding agglomeration and preventing their precipitation from the reaction media.[27] The stabilizers used in hydrogenation reactions are shown in Scheme 1. The hydrogenation of AN with Ru-NPs lead to the formation of trietylamine with high selectivity (>92 %), see Fig. 1. Other minor products, such as diethylamine, were detected in low yield. The presence of ammonia conrmed the occurrence of a condensation reaction in agreement with the formation of a tertiary amine. As expected, the use of a mercury drop for the same

experiment resulted in a sharp conversion drop, in agreement with the heterogeneous nature of the hydrogenation system.[28] A similar experiment carried out without the use of any stabilizer selectively produced trietylamine, but in lower yield (22%). The conversion obtained on this reaction can be related to the fact that TEA has also been reported to be a stabilizer for other metal NPs such as Fe-NPs.[29] However, in this case, such NPs were obtained with a wide distribution diameter (see Fig. 2A), compared with the ones obtained with SEH and SDS (see Fig. 2B and 2C). Particularly, SDS, an alcohol-type stabilizer,[30] allows a narrower diameter distribution and yields a higher conversion for AN. This hydrogenation reaction was assessed for other aliphatic nitriles using [Ru3(CO)12] as a NPs precursor, under a variety of reaction conditions summarized in Table 1. The reactivity found in aliphatic nitriles is indicative of a reduction to the corresponding amines, with a high selectivity to the tertiary amine (Table 1, entry 1). To the best of our knowledge, this result has not a precedent for ruthenium, since it is known that both homogeneous[5,31,32] and heterogeneous[33] Ru-based catalysts regularly show selectivity to primary amines. A possible explanation for this result might be related with the increased activity of the Ru-NPs due to their small size (23 nm) and

Table 1. Hydrogenation of aliphatic nitriles with ruthenium nanoparticles


PH2 (psi)

Conv. (%) 5

Selectivity (%) 6 6.5 19.2 27.9 30.2 7 92.1 77.2 69.8 63.9

1 2 3 4

-Me -Me -Et -Et

350 700 350 700

46.34 41.02 49.11 48.87

1.2 3.6 0.10 2.5

All reactions were carried out for 3 days with 0.004 mol% of NPs precursor.

Table 2. Hydrogenation of AN using Ru-NPs with a variety of stabilizing agents


Stabilizer (equiv)

Conv. (%) 5

Selectivity (%) 6 0 2.01 11.0 0 2.6 7 100 98 87.7 100 94.7

1 2 3 4 5

None 1 (0.1) 2 (4) 3 (5) 4 (5)

31.5 39.9 43.3 39.8 34.1

0 0 0.1 0 2.6

All reaction were carried out for 5 d, using 0.0156 mmol of the corresponding ruthenium nanoparticles precursor. All yields were determined by GC-MS and caracterized by NMR.

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C. ORTIZ-CERVANTES, I. IYAEZ AND J. J. GARCA consequently, increased active surface. Also note, the use of higher pressures (700 psi) in entries 2 and 4 resulted in the enhancement on the yield of secondary and primary amines over the tertiary amine due to the involved pressure-dependent reactions, related with the equilibrium between primary, secondary and tertiary amines with free ammonia.[13] Alternatively, we speculate on an increased saturation of the metal surface because of a higher amount of hydrogen, making the catalyst less active and consequently less prone to produce the tertiary amine. In order to assess the best stabilizer for the alkyl-nitrile hydrogenation, AN was chosen as substrate for that purpose, along with the stabilizers depicted on Scheme 1, these results are summarized in Table 2. As can be seen in the table, the formation of triethylamine is roughly the same among all the used stabilizers, nevertheless, when SDS was employed, the activity was slightly improved under the same reaction conditions (entry 3, Table 2). Also noteworthy, on entry 1, a mediumto-low conversion to the tertiary amine was obtained, although with an excellent selectivity (100%), without using any stabilizer at all. This is a proof of the higher preference of the Ru-NPs to produce tertiary amines. The use of a stabilizer, slightly decreases such selectivity, although increases the conversion. TEM determinations were used to characterize the produced Ru-NPs. Figure 2A shows NPs with the highest size dispersion, which turned out to be the less active. Their sizes vary widely between one to several tens of nanometers, though, the most catalytically active were in the range of 1 to 4 nm, i.e. they contain a few tens of atoms, which, conversely, are more supercially active in catalytic transformations.[16] On using higher amounts of all the different stabilizers, the selectivity of AN conversions is similar. Nonetheless, the selectivity toward the tertiary amine was slightly lower (see Fig. 3). Since the use of SDS allowed the best activity, the effect of different amounts of this stabilizer was assessed. As can be seen on Fig. 4, there is a change in the agglomeration and diameter Ru-NPs on varying the amounts of SDS employed. When 15 equiv of SDS were added into the reaction, the corresponding NPs showed less agglomeration, yet the diameter increases. The hydrogenation of an alkyldinitrile such as ADN using Ru-NPs always produced complex mixtures of amines both at 300 psi of H2 and 800 psi in THF for 3 days, with conversions of around 40%. To extend the scope of this reaction, BN was hydrogenated. As a general trend, it was necessary to use higher temperatures than that used for alkyl nitriles. To note, Beller and coworkers used the same catalytic precursor at 725 psi and 80  C with no relevant catalytic activity.[5] Unless otherwise indicated, the reactions in Table 3 were carried out under neat conditions, i.e. BN acts as reagent and solvent. Noteworthy, most of these reactions yielded mixtures of variable composition containing both primary (8) and secondary amines (9), along with the corresponding imine (10). In many of the experiments, the

Figure 3. Hydrogenation of AN with Ru-NPs using 0.004% mol of [Ru3 (CO)12] as NPs precursor and different amounts of SDS at 140  C with 350 psi of H2 pressure for 5 days

Figure 4. TEM images (50 nm scale) of ruthenium nanoparticles from 2, taken at different amounts of 2: (A) 2.5 equiv, (B) 8 equiv, (C) 15 equiv

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Entry 1 2 3 4 5 6b

t(d) 3 3 1 3 3 1

p(psi) 900 900 900 900 250 800

T( C) 290 260 260 260 260 140

Conv. (%) 8 100 99.0 73.9 94.7 59.6 30.6 56.6 19.7 2.4 14.6 7.0 0

Selectivity (%) 9 23.3 20.8 30.5 18.0 11.4 56.2

10 20.1 29.8 47.4 37.1 47.4 2.9 (TBA: 37.2)

All reactions carry out with 0.008 mmol of [Ru3(CO)12], 5 equiv of SDS as stabilizer, yields were determined by GC-MS. TBA: tribenzylamine. a Using THF as solvent. b Using 1.5 equiv of SDS.

Here, the high activity of Ru-NPs allowed the production of tertiary amines. In contrast, the BN hydrogenation was achieved with Ru-NPs on using relatively higher pressures and temperatures to yield primary and secondary amines and imines, in high conversions but with lower selectivity. Current studies are underway to improve the selectivity of these and other related aromatic and hetero aromatic nitriles.

We thank CONACYT (0178265) and DGAPA-UNAM (IN-201010) for their nancial support to this work. We thank Ivn PuenteLee (USAI-UNAM) for TEM determinations. C. O.-C also thanks CONACYT for a graduate studies grant.

Figure 5. Effect of temperature for AN hydrogenation

production of the tertiary amine was not observed (entries 1 to 5). It is known that the use of a polar solvent[34] or the addition of water increases the production of primary amines.[35] Hence, the use of THF favors the primary amine (8) (entry 1). It is worth mentioning that on using a lower temperature and a lower amount of SDS, the selectivity to secondary and tertiary amines is increased (Table 3, entry 6). This result is consistent with the ndings above discussed for alkyl-nitriles, i.e. the use of a lower temperature and low amounts of stabilizer favor the production of tertiary amines, probably due to a reduced agglomeration at lower temperatures and, consequently, an increase in the reactivity. Therefore, we performed a study to assess the effect of temperature for AN hydrogenation, see Fig. 5. The results are in agreement with the expected increased agglomeration on increasing the temperature, as a result, tertiary amines are favored at lower temperatures and secondary and primary amines at higher temperatures.

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It has been shown that the use of ruthenium NPs of 23 nm diameter are active in the catalytic hydrogenation of aliphatic nitriles and displays a sharp difference in selectivity with other homogeneous and heterogeneous ruthenium-based catalysts.

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