Iron nanoparticles are synthesized and size characterized using HRTEM, FESEM, and XRD. Polyethylene glycol(PEG), carboxymethyl cellulose (CMC), and poly N-vinyl pyrrolidone (PVP) are used as nanoparticle stabilizers. The sizes of Fe nps are found to be 9?nm, 14?nm, and 17?nm?±?1?nm corresponding to PEG, CMC, and PVP stabilizers, respectively. The three different iron nanoparticles (Fe nps) prepared are used as catalysts in the hydrogenation reaction of various substituted aromatic ketones to alcohols with NaBH4. The progress of the reaction was monitored using time variance UV spectra. Kinetic plots are made from the absorbance values and the pseudo first order rate coefficient values are determined. Catalytic efficiency of the Fe nps is obtained by comparing the pseudo first order rate coefficient values, times of reaction, and % yield. Fe-PEG nps was found to act as better catalyst than Fe-CMC nps and Fe-PVP nps. Also, effects of substituents in the aromatic ring of ketones reveal that +I substituents are better catalysed than –I substituents. 1. Introduction Reduction reactions of carbonyl compounds to primary and secondary alcohols possess one of the important classes of organic reactions that are well used in synthetic chemistry [1–5]. Such reactions find immense applications in chemical industries related to fine chemicals, pharmaceuticals, perfumes, and agrochemicals. Transition metal catalyzed reduction reactions are considered as popular substitutes of platinum metal based catalysts. Cost effectiveness, abundance, stability, recyclability, environmentally benign, and relatively nontoxic are some of the reasons for the important role of tranisition metals in catalysis. Decades of research involve traditional catalysts for ketone hydrogenation reactions involving precious metals and their coordination complexes [6–12]. Rhodium and ruthenium complexes using chiral phosphines and amines as ligands show excellent catalytic activity towards asymmetric hydrogenation of prochiral ketones and other carbonyl compounds. However, these catalysts have limited applications because of their high cost and difficulty in the separation of products from chiral catalyst. There have been several attempts to develop iron catalysts for these kinds of reactions, because these would be cheaper and nontoxic [13, 14]. In this regard, Chirik’s, Beller’s, and Nishiyama’s groups have recently reported useful iron catalysts for the hydrosilation of aldehydes and ketones [7, 15] and their transfer hydrogenation. Efforts to find catalysts that do not require noble metals are
References
[1]
J. W. Bae, S. H. Lee, Y. J. Jung, C. O. M. Yoon, and C. M. Yoon, “Reduction of ketones to alcohols using a decaborane/pyrrolidine/cerium(III) chloride system in methanol,” Tetrahedron Letters, vol. 42, no. 11, pp. 2137–2139, 2001.
[2]
Y. Ni and J. H. Xu, “Biocatalytic ketone reduction: a green and efficient access to enantiopure alcohols,” Biotechnology Advances, vol. 30, no. 6, pp. 1279–1288, 2012.
[3]
M. Aitali, S. Allaoud, A. Karim, C. Meliet, and A. Mortreux, “Enantioselective reduction of aromatic ketones catalysed by chiral ruthenium(II) complexes,” Tetrahedron Asymmetry, vol. 11, no. 6, pp. 1367–1374, 2000.
[4]
W. Kroutil, H. Mang, K. Edegger, and K. Faber, “Recent advances in the biocatalytic reduction of ketones and oxidation of sec-alcohols,” Current Opinion in Chemical Biology, vol. 8, no. 2, pp. 120–126, 2004.
[5]
A. Zanotti-Gerosa, W. Hems, M. Groarke, and F. Hancock, “Ruthenium-catalysed asymmetric reduction of ketones,” Platinum Metals Review, vol. 49, no. 4, pp. 158–165, 2005.
[6]
R. Langer, G. Leitus, Y. Ben-David, and D. Milstein, “Efficient hydrogenation of ketones catalyzed by an iron pincer complex,” Angewandte Chemie, vol. 50, no. 9, pp. 2120–2124, 2011.
[7]
N. S. Shaikh, S. Enthaler, K. Junge, and M. Beller, “Iron-catalyzed enantioselective hydrosilylation of ketones,” Angewandte Chemie, vol. 47, no. 13, pp. 2497–2501, 2008.
[8]
N. Meyer, A. J. Lough, and R. H. Morris, “Iron(II) complexes for the efficient catalytic asymmetric transfer hydrogenation of ketones,” Chemistry, vol. 15, no. 22, pp. 5605–5610, 2009.
[9]
R. Langer, M. A. Iron, L. Konstantinovski et al., “Iron borohydride pincer complexes for the efficient hydrogenation of ketones under mild, base-free conditions: synthesis and mechanistic insight,” Chemistry, vol. 18, no. 23, pp. 7196–7209, 2012.
[10]
T. Ohkuma, H. Ooka, H. Shohei, T. Ikariya, and R. Noyori, “Practical enantioselective eydrogenation of Aromatic Ketones,” Journal of the American Chemical Society, vol. 117, pp. 2675–2676, 1995.
[11]
C. A. Sandoval, T. Ohkuma, K. Mu?iz, and R. Noyori, “Mechanism of asymmetric hydrogenation of ketones catalyzed by BINAP/1,2-diamine-ruthenium(II) complexes,” Journal of the American Chemical Society, vol. 125, no. 44, pp. 13490–13503, 2003.
[12]
T. C. Johnson, W. G. Totty, and M. Wills, “Application of ruthenium complexes of triazole-containing tridentate ligands to asymmetric transfer hydrogenation of ketones,” Organic Letters, vol. 14, no. 20, pp. 5230–5233, 2012.
[13]
S. Gaillard and J. L. Renaud, “Iron-catalyzed hydrogenation, hydride transfer, and hydrosilylation: an alternative to precious-metal complexes?” ChemSusChem, vol. 1, no. 6, pp. 505–509, 2008.
[14]
J. F. Sonnenberg, N. Coombs, P. A. Dube, and R. H. Morris, “Iron nanoparticles catalyzing the asymmetric transfer hydrogenation of ketones,” Journal of the American Chemical Society, vol. 134, no. 13, pp. 5893–5899, 2012.
[15]
H. Nishiyama and A. Furuta, “An iron-catalysed hydrosilylation of ketones,” Chemical Communications, no. 7, pp. 760–762, 2007.
[16]
C. Rangheard, C. de Julián Fernández, P. H. Phua, J. Hoorn, L. Lefort, and J. G. De Vries, “At the frontier between heterogeneous and homogeneous catalysis: Hydrogenation of olefins and alkynes with soluble iron nanoparticles,” Dalton Transactions, vol. 39, no. 36, pp. 8464–8471, 2010.
[17]
P. H. Phua, L. Lefort, J. A. F. Boogers, M. Tristany, and J. G. De Vries, “Soluble iron nanoparticles as cheap and environmentally benign alkene and alkyne hydrogenation catalysts,” Chemical Communications, no. 25, pp. 3747–3749, 2009.
[18]
V. Kelsen, B. Wendt, S. Werkmeister, K. Junge, M. Beller, and B. Chaudret, “The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds,” Chemical Communications, vol. 49, no. 33, pp. 3416–3418, 2013.
[19]
A. Welther, M. Bauer, M. Mayer, and A. JacobivonWangelin, “Iron(0) particles: catalytic hydrogenations and spectroscopic studies,” ChemCatChem, vol. 4, no. 8, pp. 1088–1093, 2012.
[20]
R. Hudson, A. Rivière, C. M. Cirtiu, K. L. Luska, and A. Moores, “Iron-iron oxide core-shell nanoparticles are active and magnetically recyclable olefin and alkyne hydrogenation catalysts in protic and aqueous media,” Chemical Communications, vol. 48, no. 27, pp. 3360–3362, 2012.
[21]
M. Stein, J. Wieland, P. Steurer, F. T?lle, R. Mülhaupt, and B. Breit, “Iron nanoparticles supported on chemically-derived graphene: catalytic hydrogenation with magnetic catalyst separation,” Advanced Synthesis and Catalysis, vol. 353, no. 4, pp. 523–527, 2011.
[22]
K.-C. Huang and S. H. Ehrman, “Synthesis of iron nanoparticles via chemical reduction with palladium ion seeds,” Langmuir, vol. 23, no. 3, pp. 1419–1426, 2007.
[23]
L. Guo, Q. J. Huang, X. Y. Li, and S. Yang, “PVP-coated iron nanocrystals: anhydrous synthesis, characterization, and electrocatalysis for two species,” Langmuir, vol. 22, no. 18, pp. 7867–7872, 2006.
[24]
R. Singh, V. Misra, and R. P. Singh, “Synthesis, characterization and role of zero-valent iron nanoparticle in removal of hexavalent chromium from chromium-spiked soil,” Journal of Nanoparticle Research, vol. 13, no. 9, pp. 4063–4073, 2011.
[25]
J. Santhanalakshmi and L. Parimala, “The copper nanoparticles catalysed reduction of substituted nitrobenzenes: Effect of nanoparticle stabilizers,” Journal of Nanoparticle Research, vol. 14, no. 9, article 1090, 2012.
[26]
Y. Li, E. Boone, and M. A. El-Sayed, “Size effects of PVP-Pd nanoparticles on the catalytic Suzuki reactions in aqueous solution,” Langmuir, vol. 18, no. 12, pp. 4921–4925, 2002.