Ruthenium nanoparticle-intercalated montmorillonite clay for solvent-free alkene hydrogenation reaction

Article abstract of DOI:10.1039/c4ra12324g

Well-characterized, ruthenium nanoparticle-intercalated montmorillonite clay was used as a catalyst in solvent-free alkene hydrogenation reactions and the corresponding products were obtained in good yields. The catalytic activity of ruthenium nanoparticle-intercalated montmorillonite clay was successfully tested with 16 different functionalized and non-functionalized alkenes. Apart from alkene reduction, the ruthenium nanoparticle-intercalated montmorillonite clay was also tested in Wittig-type reactions for obtaining dehydrobrittonin A, an important intermediate for the synthesis of brittonin A. Ruthenium nanoparticle-intercalated montmorillonite clay was found to be active in the synthesis of dehydrobrittonin A and brittonin A. The ability to recycle the catalyst nine times, together with low catalyst loading, high catalytic activity and catalytic selectivity were noteworthy advantages of the proposed protocol.

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Page 1 of 11
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DOI: 10.1039/C4RA12324G
Ruthenium nanoparticles intercalated montmorillonite clay for
solvent free alkene hydrogenation reaction
Vivek Srivastava
Applied Sciences: Chemistry, NITT University, NHꢀ8 Jaipur/Delhi Highway, Neemrana
(Rajasthan) Pin Code: 301705
Contact Number: 0+911494302423, email id: vivek.shrivastava@niituniversity.in
Abstract
Well characterized ruthenium nanoparticles intercalated montmorillonite clay was used as a catalyst for
solvent free alkene hydrogenation reaction and the corresponding products were obtained in good yield.
The catalytic activity of ruthenium nanoparticles intercalated montmorillonite clay was successfully
tested for 16 different functionalized and nonꢀfunctionalized alkenes. Apart from alkene reduction, the
ruthenium nanoparticles intercalated montmorillonite clay was also applied for Wittigꢀtype reaction for
obtain dehydrobrittonin A, an important intermediate for the syntheses of brittonin A. Ruthenium
nanoparticles intercalated montmorillonite clay was found active for the synthesis of dehydrobrittonin A
and brittonin A. 9 times catalyst recycling, low catalyst loading, high catalytic activity and catalytic
selectivity were the noteworthy outcomes of the proposed protocol.
Keywords: ruthenium nanoparticles, Montmorillonite clay, hydrogenation reaction, dehydrobrittonin A,
brittonin A, solvent free reaction, alkene hydrogenation
1. Introduction
Ru nanoparticles are well known catalyst for a wide range of organic reactions such as hydrogenation,
hydrogenolysis, nitrile hydration, epoxidation, FischerꢀTropsh synthesis etc. [1,2] Various organicꢀ
inorganic supports such as activated carbon [3], SiO2 [4, 5], Al2O3 [6, 7], zeolite [8, 9], ionic liquids [10,
11] and polymers [12] have been reported to support the Ru nanoparticles to utilize them as an effective
heterogeneous catalyst. Montmorillonite clay (MMT) is one of the important materials for supporting the
catalysts due to its unique phytochemical properties like high cation exchange capacity and good swelling
properties. [13ꢀ15] Furthermore, reactions that are catalyzed by MMT are extremely easy to “workꢀup”
since the clay does not dissolve in the reaction medium (solvent), it can simply be filtered away when the
reaction is complete. MMT has been the most frequently used support to intercalate different metal ions
and is further tested as catalyst in various organic transformations such as oxidation, reduction,
transesterification, coupling reactions, etc. [15] Metal intercalated MMTs are well documented catalyst
for the selective hydrogenation reaction of different organic compounds. Rh3+, Ru3+ or Pd3+ ions are still
difficult to exchange completely by the interlayer cations of MMT clay. [16] Few reports are available for
exchanging the Ru3+ ions within the interlayer spacing of MMT clay. Recently, Liu et al reported the
synthetic protocol for Ru nanoparticle immobilized MMT clay using task specific ionic liquid [IL]. [17]
In this report, the firstly ionic liquid was exchanged with exchangeable ions of MMT and then Ru3+ ions
were loaded onto the ILꢀexchanged MMT clay. This catalytic system was successfully tested as a catalyst
for the benzene hydrogenation reaction.
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Hydrogenation of alkenes is an important synthetic tool for achieving the different biologically important
molecules with good yield. [16ꢀ21] Several hydrogenating reagents such as NiCl2ꢀNaBH4, PdCl2ꢀNaBH4
polyethylene glycol (PEG)ꢀCH2Cl2, CoCl2ꢀNaBH4 etc., have been tested as hydrogenation systems. [22]
Along with toxicity, these systems also suffered with long reaction time, high catalyst loading, costly
starting materials and tedious reaction protocol of these hydrogenating reagents.
In this paper, we are offering the controlled synthesis of Ru metal nanoparticles (Ru MNPs) by
exchanging [Ru (NH3) ]+3 ions for interlayer Na+, K+ or Ca2+ ions. The exchanged Ru3+ ions were
6
successively reduced by sodium boron hydride to Ru MNPs which were intercalated into MMT clay
which were successively reduced sodium boron hydride to Ru MNPs intercalated into MMT clay. High
dispersion of Ru3+ ions were successively reduced by sodium boron hydride to Ru MNPs which were
intercalated into MMT clay followed by ion exchange process. Ruthenium nanoparticles intercalated
montmorillonite clay Ru MMT was used to hydrogenate cyclic as well as acyclic olefins under different
reaction conditions such as different temperature, pressure, solvent systems, etc., to obtain the
corresponding reaction products with good yield.
2. Experimental
Reagent Plus® grade ruthenium(III) chloride hydrate was purchased from Aldrich. ReagentPlus® and
extra pure grade alkenes were purchased from Aldrich and Acros chemicals. Lindlar catalysts, 5% Pt on
carbon and Renney nickel were supplied Vinneth chemicals, India as free samples. Nuclear Magnetic
Resonance (NMR) spectra were recorded on a standard Bruker 300WB spectrometer with an Avance
1
console at 400 and 100 MHz for H and 13C NMR, respectively. Z/E ratio determined from the crude
1
product H NMR spectroscopy. The commercial sodium montmorillonite clay (Cloisite®Na) used in the
present study was supplied by Southern Clay Products, Gonzales, Texas (USA). The cation exchange
capacity (CEC) of sodium montmorillonite (NaꢀMMT) is 92.6 meq/100 g as reported by suppliers. All the
hydrogenation reactions were carried out in a 100 mL stainless steel autoclave (Amar Equipment, India).
The Ru MMT catalyst material was characterized by TEM (Hitachi Sꢀ3700N) and Energyꢀdispersive Xꢀ
ray spectroscopy (EDX) (Perkin Elmer, PHI 1600 spectrometer). The specific surface area (BET) of the
catalyst was determined on a Micrometrics Flowsorb III 2310 instrument. The catalyst was preꢀtreated at
120oC under vacuum for over 2h to desorb contaminating molecules (mainly water) from the catalyst
surface for the determination of BET.
2.1 Catalysts Preparation
The [Ru (NH3) 6] Cl3 solution was prepared by reacting a solution containing equimolar amounts of water
and ammonia with RuCl3. 3H2O.[23, 24] The solvent was evaporated under mild reduced pressure on the
steam bath until only a faint odor of ammonia gas was noticeable. The resulting pale yellow solution was
filtered and allowed to cool in ice bath (5ꢀ10oC). The neat MMT clay (without any treatment or
modification) was dispersed in 250mL deionized water and stirred to facilitate complete dispersion for 2
hours at room temperature. Then, 40 mL hexamine ruthenium (III) solution (0.92 meq/g of MMT) were
added under constant stirring at room temperature (303K) with an addition rate of 0.5 mL/min to obtain
obtain [Ru (NH3)6]ꢀMMT, which was subsequently reduced by NaBH4 at room temperature. A grayish
black dispersion was formed. Ru MMT was filtered, washed, dried at 313 K for the next 3 hours in a
vacuum oven and grounded to fine powders using a pestle and a mortar.
2

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2.2 Hydrogenation of alkenes and catalyst recycling
The autoclave (1mL) was charged with alkenes (2mL) and catalyst (0.1g). Solvent, additive and hydrogen
source (except hydrogen gas) was added as required. After closing the autoclave, the air was replaced
with hydrogen gas (10 bar), then the reactants were allowed to react at 80oC for 1 hour. After that, the
autoclave was cooled by supplying cold water (2ꢀ5oC). The reaction product was isolated with diethyl
ether (5 x2mL). The isolated product was further purified by a column chromatography using ethyl
acetate/hexane solvent system (15:85). The catalytic system was further dried under reduced pressure at
50oC for 30 minutes and recycled for the next run.
2.3 One pot Wittig olefination reaction
50 mL round bottom flask was charged with 1.6 M nꢀBuLi (6.25 µL,1.0 mmol) which was added
dropwise to a suspension of corresponding methoxylated benzyltriphenylphosphonium halide (1.5 mmol)
in dry THF (2 mL), at 0oC under argon atmosphere to obtain the corresponding ylide. After 20 minutes,
Ru MMT (0.1g) was added to the combined reaction mass of the (3,4,5ꢀtrimethoxyphenyl) methanol (1
mmol) and the initially prepared ylide suspension. The reaction mixture was allowed to stir for next 1
hour at 80oC. The resulting reaction product was isolated by diethyl ether washing (5 x2mL) and the
reaction product was further purified with a column column chromatography using ethyl acetate/hexane
solvent system (10:90) to obtain product dehydrobrittonin A.
3. Result and Discussion
A small to medium angle Xꢀray scattering (SAXS) analysis was carried out to study the change between
the basal spacing of Ru MMT with respect to neat MMT (Figure 1). The basal spacing of neat MMT was
d001=12.95Å, while after the exchange of Ru ions within the interlayer spacing of MMT, a significant
increase was observed and the Ru MMT was enlarged to d001=14.96Å. Such increase between the basal
spacing of MMT represents the presence of Ru ions between the basal spacing of MMT. It is worth noting
here, the small characteristic peak for Ru nanoparticles in the XRD data, represents the existence of Ru
MNPs (either very small or amorphous) (Figure 2).
Insert figure 1 here
The average TEM particle size of Ru is 20.5±2 nm in RuꢀMMT. The TEM image clearly reveals the
agglomeration of Ru MNPs on MMT (Figure 3 a & b). The presence of Ru species within the interlayer
spacing of MMT clay was also confirmed by using high resolution transmission electron microscopy
(HRTEM) analysis (Figure 4). We embedded Ru MMT in epoxy resin in order to get a uniform solid
specimen and cut the specimen using ultraꢀ microtome to achieve an ultraꢀthin section of Ru MMT.
Ruthenium wt% in catalyst was calculated using inductively coupled plasma atomic emission
spectrometer (ICPꢀAES, ARCOS from M/s. Spectro, Germany). 0.1 g of sample was digested in a
minimum amount of conc. HNO3 with heating, and volume made up to 10 ml. Theoretical (cation
exchange capacity) and an experimental (ICPꢀAES) method was used to calculate the amount of Ru
species in MMT. Both theoretical and experimental values were found to be in good agreement, and 2.5
wt% Ru MMT. [22] This protocol also minimizes the loss of Ru nanoparticles during the synthesis of Ru
MMT.
Insert figure 2 here
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The specific surface area of Ru MMT was measured by nitrogen adsorption using the BET method. This
is an important characteristic of heterogeneous catalyst and liable to change during preparation,
conditioning, in use and particularly if exposed to excessive temperatures. The specific surface area of
neat MMT (82 m2/ g) was increased up to 85 m2/ g for Ru MMT clay.
A primary study to check the catalytic activity of Ru MMT was carried out using hydrogenation of
allylbenzene as a model test reaction to optimize the reaction conditions and all the corresponding results
were summarized in table 1, entries 1ꢀ19. The best test result was obtained while stirring the allybenzene
and Ru MMT without solvent at 80oC for 1 hour under hydrogen atmosphere (Table 1, Entries 1).
Three different hydrogen sources were screened to replace the hydrogen gas, but as per the corresponding
results the high yield only obtained with hydrogen gas (Table 1, Entries 1, 15 and 16). On the basis of
experimental results (Table 1, Entries 1ꢀ19), Ru MMT catalyzed alkene hydrogenation reaction was
totally dependent on temperature, reaction time and the pressure of the hydrogen gas because once any
one of the factor deviated, the lower catalytic response of Ru MMT was observed on the corresponding
product yield (Table 1, Entries 1ꢀ14). We also checked the catalytic behavior of Ru MMT in the presence
of additives and the results were documented in Table 1, entries 18ꢀ19. Raney nickel and other catalysts
were also evaluated under optimized reaction condition, but no noteworthy results (Table 1, Entries 20ꢀ
22) were obtained.
Insert Table 1 here
Ru MMT was further evaluated for the hydrogenation of 13 different functionalized and nonꢀ
functionalized alkenes (Table 2, Entries 1ꢀ13). Terminal alkenes were easily reduced to the corresponding
alkanes in quantitative yield (Table 2, Entry 1). The same behavior was observed with transꢀstilbene as
well as for αꢀmethylstyrene and we easily isolated their corresponding products in good yield (Table 2,
entries 2ꢀ3). Further, we studied hydrogenation of functionalized olefins (entries 4ꢀ13). Ru MMT was
found catalytically sound for both terminals as well as for internal unsaturated esters and offers their
corresponding product in high yield. Interestingly, no transesterification was detected while performing
the hydrogenation reaction of ethyl 6ꢀheptenoate (Table 2, entries 4). In the presence of Ru MMT, not
only electronꢀrich aromatic 3,4ꢀdimethoxystyrene and isosafrole were also nicely reduced in high isolated
yields (entries 7 and 8) but also allylic alcohols, with either a monosubstituted or geminal C=C bond were
nicely reduced without any isomerization of corresponding reaction products, (Table 2, Entries 9 and 10).
It is significant to write here that transitionꢀmetal catalysts, during catalytic hydrogenation, encourage
such type of type of isomerization. Monoterpene (±)ꢀlinalool [25], which holds both a monoꢀ as well as
triꢀsubstituted C=C bond, was easily altered into the saturated tertiary alcohol 3,7ꢀdimethyloctanꢀ3ꢀol
(tetrahydrolinalool) in moderate yield (Table 2, Entries 11). The reduction of allyl benzyl ether and Nꢀ
allylcyclohexylamine were easily taken care by RuꢀMMT, for both substrates the desired products were
obtained in quantitative yield (Table 2, entries 12 and 13).
Insert table 2 here
The flexibility of Ru MMT was also checked for the synthesis of two unique biologically important
products. First, we performed the synthesis of brittonin A, which was isolated from Frullania brittoniae
subsp. truncatifolia (F. F. muscicola). [26] The brittonin A obtained as a hydrogenated product of
dehydrobrittonin A in high yield. [27] To the best of our knowledge, this is the first solvent free Ru
4

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MMT catalyzed Wittigꢀtype reaction of properly substituted benzyl alcohols and phosphorus ylides, in
which there is no standard redox step was used and we synthesized dehydrobrittonin A with moderate
yield and the process also displayed low diastereoselectivity, mainly in favor of the E diastereoisomer.
[28] In our study, a maximum ca. 1:4 Z/E ratio of diastereomeric dehydrobrittonin A was obtained while
Nickel nanoparticles offered the same reaction product with comparatively low diastereomeric Z/E ratio
(46:54) (Scheme 1).
Insert scheme 1 here
After getting delightful results of Ru MMT catalyzed hydrogenation of different alkenes, we also tested
the stability of Ru MMT in catalyst recycling experiment for our model test reaction (hydrogenation of
allylbenzene) and recycled Ru MMT up to 9 runs without any significant loss of yield (Figure 3).
Potential Ru leaching into the reaction mixture was also analyzed with ICP/OES analysis. For this
purpose, samples were taken through a syringe filter (Whatman Puradisc 4, 4 mm diameter, 0.45 ꢁm,
PTFE) during our model test reaction (hydrogenation of allylbenzene). Volatile impurities were
evaporated, and the residue was dissolved in HNO3. The analysis of these samples with ICPꢀ AES showed
that the Ru concentration in the reaction solution was less than the detection limit (i.e., 50 ppb). The same
result was obtained when the complete reaction mixture of model test reaction was filtered, the solvent
was evaporated, and the residue was dissolved in HNO3. Both findings indicate that virtually no Ru
leaches from the Ru MMT into the solution.
Insert figure 3 here
4. Conclusion
The synthetic protocol for Ru nanoparticles intercalated into MMT is represented in this manuscript using
different analytical techniques for Ru MMT. Physiochemical parameters were investigated using different
sophisticated analytical techniques for Ru MMT. TEM image showed agglomeration of Ru nanoparticles
in MMT and subjugated that the average particle size of Ru nanoparticle was 20.5±2 nm. Catalytic
activity of well characterized Ru MMT was tested for 13 types of functionalized and nonꢀfunctionalized
alkenes. All the alkenes were nicely hydrogenated under solvent free condition with good yield of
corresponding reaction products in good yield. The catalytic activity of Ru MMT was also exploited for
the synthesis of natural product brittonin A as well as for Wittigꢀtype reaction to obtain dehydrobrittonin
A. Both products were obtained in quantitative yield. Apart from that low catalyst loading, no use of
additives, wide substrate scope, solvent free approach, easy product isolation and catalyst recycling up to
9 times are the major outcomes of this proposed protocol.
References
1. P. Lara, K. Philippot and B. Chaudret, ChemCatChem 2013, 5, 28–45.
2. J. Gavnholt and J. Schiøtz, Phys. Rev. B 2008, 77, 1ꢀ10.
3. E. J. GarcíaꢀSuárez, P. Lara, A. B. García and K. Philippot, Recent Pat Nanotechnol. 2013, 2ꢀ 247ꢀ264.
4. A. I. Carrillo, L. C. Schmidt, M. L. Marínab and J. C. Scaiano Catal. Sci. Technol. 2014,4, 435ꢀ440.
5. R. B. N. Baig and R. S. Varma, ACS Sustainable Chem. Eng. 2013, 1, 805–809.
5

RSC Advances
Page 6 of 11
View Article Online
DOI: 10.1039/C4RA12324G
6. I. Balinta, A. Miyazakib and K.ꢀi. Aika, Journal of Catalysis 2002, 207, 66ꢀ75.
7. I. Balint, A. Miyazakib and K.ꢀi. Aikab, Chem. Commun. 2002, 630ꢀ631.
8. J. Sun, X. Li, A. Taguchi, T. Abe, W. Niu, P. Lu, Y. Yoneyama and N. Tsubaki, ACS Catal. 2014, 4, 1–8.
9. D. K. Mishra, A. A. Dabbawala and J.ꢀS. Hwang, Journal of Molecular Catalysis A: Chemical 2013, 376,
63ꢀ70.
10. L. M. Rossi, J. DupontI, G. MachadoI, P. F. P. Fichtner, C. Radtke, I. J. R. Baumvol and S. R. Teixeira, J.
Braz. Chem. Soc. 2004, 15, 904ꢀ910.
11. G. Salas, P. S. Campbell, C. C. Santini, K. Philippot, M. F. C. Gomesd and A. A. H. Pádua, Dalton Trans.
2012,41, 13919ꢀ13926.
12. D. K. Mishra and A. A. Dabbawala, J.ꢀ S. Hwang, Catalysis Communications 2013, 41, 52ꢀ55.
13. A. Jhaa, A.C. Garadea, M. Shiraib, C.V. Rode, Applied Clay Science 2013, 74, 141ꢀ146.
14. J. M. Adams, T. V. Clapp and D. E. Clement, Clay 1983, 18, 411–421.
15. V. Srivastava, Bulletin of the Catalysis Society of India 2012, 11, 56ꢀ77.
16. A.B. Boricha, H.M. Mody, H.C. Bajaj and Raksh V. Jasra, Applied Clay Science 2006, 31, 120ꢀ125.
17. H. Xu, K. Wang, H. Zhang, L. Hao, J. Xua and Z. Liu, Catal. Sci. Technol. 2014, 4, 2658ꢀ2663.
18. C. Morina, D. Simonb and P. Sautet, Surface Science 2006, 600, 1339ꢀ1350.
19. M. Guerrero, N. T. T. Chau, S. Noël, A. DenicourtꢀNowicki, F. Hapiot, A. Roucoux, E. Monflier, and K.
Philippot, Current Organic Chemistry 2013, 17, 364ꢀ399.
20. M. Cano, A. M. Benito, W. K. Masera and E. P. Urriolabeitia, New J. Chem. 2013,37, 1968ꢀ1972.
21. C. P. Ruas, D. K. Fischer and M. A. Gelesky, Journal of Nanotechnology 2013, 2013, 1ꢀ6.
22. P. K. Sharma, S. Kumar, P. Kumar and Poul Nielsen, Tetrahedron Letters 2007, 48, 8204ꢀ8708.
23. K. B. Sidhpuria, H. A. Patel, P. A. Parikh, P. Bahadur, H. C Bajaj and R. V. Jasra, Applied Clay Science
2009, 42, 386ꢀ390.
24. L. Jiao and J. R. Regalbuto, Journal of Catalysis 2008, 260, 329–341.
25. V.R. Coelhoa, J. Gianesinia, R. Von Borowskia, L. MazzardoꢀMartinsb, D.F. Martinsb, J.N. Picadaa,
A.R.S. Santosb, L.F.S. Bruma and P. Pereira, Phytomedicine 2011, 896ꢀ901.
26. Y. Asakawaa, K. Tanikawaa and T. Aratanib, Phytochemistry 1976, 15, 1057–1059.
27. F. Alonso, , P. Riente and M. Yus, Tetrahedron 2009, 65, 10637–10643.
28. F.Alonso, P. Riente and M. Yus, European Journal of Organic Chemistry 2009, 2009, 6034–6042.
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Figure 1 Small to medium angle X-ray scattering (SAXS) data for MMT and Ru MMT
Figure 2 XRD patterns of the MMT, Ru MMT (fresh), Ru MMT (used)

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a. TEM image of MMT
b. TEM image of Ru MMT
Figure 3 TEM images of MMT and RU MMT
Neat MMT
Ru MMT
Figure 4 HRTEM analysis

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OCH3
OCH3
OH
PPh3
H3CO
H3CO
OCH3
OCH3
H3CO
H3CO
Ru MMT (0.1g)
1 h, 80oC
OCH3
dehydrobrittonin A
(72% yield, Z/E= 20:80)
OCH3
OCH3
OCH3
NiNPs (1 eqs.)
THF, 24h, reflux
Ru MMT (0.1g)
80oC, 1h
OCH3
OCH3
OCH3
OCH3
H3CO
H3CO
OCH3
H3CO
H3CO
NiNPs (20 mmol)
OCH3
dehydrobrittonin A
(61% yield, Z/E= 46:54)
brittonin A
(95% yield)
i-PrOH, 76oC, 2h
OCH3
OCH3
reported procedure [25-27]
Scheme 1 Synthesis of brittonin A

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Recycling Experiment
96
95
94
93
92
91
90
Yield (%)
1st 2nd 3rd 4th 5th 6th 7th 8th 9th
run run run run run run run run run
Figure 3 Recycling test of Ru MMT for allylbenzene hydrogenation reaction

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Ruthenium nanoparticles intercalated montmorillonite clay for
solvent free alkene hydrogenation reaction
Vivek Srivastava
Applied Sciences: Chemistry, NITT University, NH-8 Jaipur/Delhi Highway, Neemrana
(Rajasthan) Pin Code: 301705