Polysilane-Supported Nickel as an Efficient Catalyst for the Hydrogenation of Aromatic Compounds

Abstract

The treatment of poly(monohydro)silane with the zero-valent nickel precursor Ni(cod)₂ (cod = 1,5-cyclooctadiene) in toluene at 100 °C leads to the formation of a heterogeneous Ni/Si catalyst that efficiently mediates the hydrogenation of various arenes and heteroarenes under reaction conditions that are relatively mild compared to conventional heterogeneous nickel-based catalysts such as Raney nickel. For instance, the hydrogenation of benzene proceeds smoothly under 8 atm of H₂ (100 °C, 24 h) to exclusively afford cyclohexane in a quantitative yield. An X-ray photoelectron spectroscopy (XPS) analysis revealed that the composition of this heterogeneous Ni/Si catalyst resembles that of nickel-silicide, albeit that the present catalyst exhibits a catalytic activity that is significantly superior to that of commercially available nickel-silicide. This heterogeneous Ni/Si catalyst can be recycled multiple times via simple centrifugation without any noticeable decrease in catalytic activity.

Keywords

Heterogeneous catalyst / Hydrogenation / Nickel / Polysilane / Aromatic compounds / Silicide / Reusable catalyst / Base metal catalyst

References

[1] (a) Nishimura, S. Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis, Wiley, New York, 2001, pp. 414-571; (b) Widegren, J. A.; Finke, R. G. A review of soluble transition-metal nanoclusters as arene hydrogenation catalysts. J. Mol. Catal. A Chem. 2003, 191, 187-207; (c) Alonso, F.; Riente, P.; Yus, M. Nickel nanoparticles in hydrogen transfer reactions. Acc. Chem. Res. 2011, 44, 379-391; (d) Wertjes, W. C.; Southgate, E. H.; Sarlah, D. Recent advances in chemical dearomatization of nonactivated arenes. Chem. Soc. Rev. 2018, 47, 7996-8017; (e) Luckemeier, L.; Pierau, M.; Glorius, F. Asymmetric arene hydrogenation: towards sustainability and application. Chem. Soc. Rev. 2023, 52, 4996-5012; (f) Chhabra, A.; Reich, S.; Shannon, T. M.; Maleczka, R. E.; Smith, M. R. Access to C(sp³)borylated and silylated cyclic molecules: hydrogenation of corresponding arenes and heteroarenes. RSC Adv. 2024, 14, 10590-10607; (g) Rayhan, U.; Kowser, Z.; Islam, M. N.; Redshaw, C.; Yamato, T. A review on the recent advances in the reductions of carbon-carbon/ oxygen multiple bonds including aromatic rings using raney Ni-AI alloy or al powder in the presence of noble metal catalysts in water. Top. Catal. 2018, 61, 560-574; (h) Wang, D. S.; Chen, Q. A.; Lu, S. M.; Zhou, Y. G. Asymmetric hydrogenation of heteroarenes and arenes. Chem. Rev. 2012, 112, 2557-2590; (i) Qi, S. C.; Wei, X. Y.; Zong, Z. M.; Wang, Y. K. Application of supported metallic catalysts in catalytic hydrogenation of arenes. RSC Adv. 2013, 3, 14219-14232.

[2] (a) Preuster, P.; Papp, C.; Wasserscheid, P. Liquid organic hydrogen carriers (LOHCs): toward a hydrogen-free hydrogen economy. Acc. Chem. Res. 2017, 50, 74-85; (b) He, T.; Pei, Q.; Chen, P. Liquid organic hydrogen carriers. J. Energy Chem. 2015, 24, 587-594; (c) Niermann, M.; Timmerberg, S.; Drünert, S.; Kaltschmitt, M. Liquid Organic Hydrogen Carriers and alternatives for international transport of renewable hydrogen. Renew. Sustain. Energy Rev. 2021, 135, 110171; (d) Niermann, M.; Beckendorff, A.; Kaltschmitt, M.; Bonhoff, K. Liquid Organic Hydrogen Carrier (LOHC)-Assessment based on chemical and economic properties. Int. J. Hydrogen Energy 2019, 44, 6631-6654; (e) Lin, A.; Bagnato, G. Revolutionising energy storage: The latest breakthrough in liquid organic hydrogen carriers. Int. J. Hydrogen Energy 2024, 63, 315-329; (f) Agyekum, E. B.; Tarawneh, B.; Rashid, F. L. State-of-the-Art review of liquid organic hydrogen carriers for hydrogen storage and transport: challenges and perspectives. Appl. Energy 2025, 400, 126555; (g) Jangir, J.; Jagirdar, B. R. Unveiling the Potential of Heterogeneous Systems for Reversible Hydrogen Storage in Liquid Organic Hydrogen Carriers. ChemSusChem 2025, 18, e202402018; (h) Allendorf, M. D.; Stavila, V.; Snider, J. L.; Witman, M.; Bowden, M. E.; Brooks, K.; Tran, B. L.; Autrey, T. Challenges to developing materials for the transport and storage of hydrogen. Nat. Chem. 2022, 14, 1214-1223.

[3] (a) Voorhees, V.; Adams, R. The Use of the Oxides of Platinum for the Catalytic Reduction of Organic Compounds. I. J. Am. Chem. Soc. 1922, 44, 1397-1405; (b) Chaston, J. C. Solid oxide of platinum and rhodium. Formation in high pressures of oxygen. Platin. Met. Rev. 1969, 13, 28-29.

[4] (a) Catalysis without Precious Metals, Ed.: Bullock, R. M., Wiley-VCH, Weinheim, 2010; (b) Peng, J. B.; Wu, F. P.; Wu, X. F. First-row transition-metal-catalyzed carbonylative transformations of carbon electrophiles. Chem. Rev. 2018, 119, 2090-2127; (c) Chen, J.; Guo, J.; Lu, Z. Recent advances in hydrometallation of alkenes and alkynes via the first row transition metal catalysis. Chin. J. Chem. 2018, 36, 1075-1109; (d) Zhang, L. H.; Mathew, S.; Hessels, J.; Reek, J. N.; Yu, F. Homogeneous catalysts based on first-row transition-metals for electrochemical water oxidation. ChemSusChem 2021, 14, 234-250; (e) Reed-Berendt, B. G.; Polidano, K.; Morrill, L. C. Recent advances in homogeneous borrowing hydrogen catalysis using earth-abundant first row transition metals. Org. Biomol. Chem. 2019, 17, 1595-1607; (f) Obligacion, J. V.; Chirik, P. J. Earth-abundant transition metal catalysts for alkene hydrosilylation and hydroboration. Nat. Rev. Chem. 2018, 2, 15-34; (g) Huang, T.; Du, P.; Lin, Y. M. Recent Advances in Photoactive First-Row Transition Metal Complexes for Organic Synthesis. Chin. J. Chem. 2025, 43, 2566-2587; (h) Chakraborty, S.; Bhattacharya, P.; Dai, H.; Guan, H. Nickel and iron pincer complexes as catalysts for the reduction of carbonyl compounds. Acc. Chem. Res. 2015, 48, 1995-2003.

[5] (a) Sabatier, P. How I Have Been Led to the Direct Hydrogenation Method by Metallic Catalysts. Ind. Eng. Chem. 1926, 18, 1005-1008; (b) Sabatier, P.; Senderens. J. B. Hydrogénations directes réalisées en présence de nickel réduit : préparation de I'hexahydrobenzène. C. R. Hebd. Séances Acad. Sci. Paris 1901, 132, 210-215.

[6] (a) Raney, M. Method of preparing catalytic material. US 1563587A, 1925; (b) Raney, M. Method of producing finely-divided nickel, US 1628190A, 1927; (c) Raney, M. Catalysts From Alloys. Ind. Eng. Chem. 1940, 32, 1199-1203; (d) Schroter, R. Neuere methoden der präparativen organischen Chemie. 13. Hydrierungen mit Raney-Katalysatoren. Angew. Chem. 1941, 54, 229-234; (e) Lieber, E.; Morritz, F. L. The Uses of Raney Nickel. Adv. Catal. 1953, 5, 417-455.

[7] Wang, R.; Zhang, M.; Zhang, J.; Yang, J. H. Supported Nickel-based Catalysts for Heterogeneous Hydrogenation of Aromatics. ChemistrySelect 2023, 8, e202302787.

[8] (a) Savva, P. G.; Goundani, K.; Vakros, J.; Bourikas, K.; Fountzoula, C.; Vattis, D.; Lycourghiotis, A.; Kordulis, C. Benzene hydrogenation over Ni/Al₂O₃ catalysts prepared by conventional and sol-gel techniques. Appl. Catal., B Environ. 2008, 79, 199-207; (b) Peyrovi, M. H.; Parsafard, N.; Mohammadian, Z. Benzene selective hydrogenation over supported Ni (nano-) particles catalysts: Catalytic and kinetics studies. Chin. J. Chem. Eng. 2018, 26, 521-528; (c) Savva, P. G.; Goundani, K.; Vakros, J.; Bourikas, K. Benzene hydrogenation over Ni/Al₂O₃ catalysts prepared by conventional and sol-gel techniques. Appl. Catal. B 2008, 79, 199-207; (d) Peyrovi, M. H.; Parsafard, N.; Mohammadian, Z. Benzene selective hydrogenation over supported Ni (nano-) particles catalysts: Catalytic and kinetics studies. Chin. J. Chem. Eng. 2018, 26, 521-528; (e) Zhao, Z.; Long, X.; Millan, M.; Yuan, G.; Cui, Z.; Dong, Z.; Cong, Y.; Zhang, J.; Li, X. The influence of carbon supports and their surface modification on aqueous phase highly selective hydrogenation of phenol to cyclohexanol over different Ni/carbon catalysts. Carbon 2023, 213, 118227; (f) Adkins, H.; Cramer, H. I. The Use of Nickel as a Catalyst for Hydrogenation. J. Am. Chem. Soc. 1930, 52, 4349-4358.

[9] (a) Suga, Y.; Sunada, Y. Organosilicon- and Organogermanium-based Ligands as Key Components of Iron Complexes with Characteristic Reactivity Patterns. Bull. Chem. Soc. Jpn. 2025, 98, uoaf092; (b) Sunada, Y.; Nagashima, H. Disilametallacyclic chemistry for efficient catalysis. Dalton Trans. 2017, 46, 7644-7655; (c) Kobayashi, Y.; Sunada, Y. Germanium hydrides as an efficient hydrogen-storage material operated by an iron catalyst. Chem. Sci. 2023, 14, 1065-1071; (d) Kobayashi, Y.; Sunada, Y. Iron Disilyl Complex as an Effective Catalyst for Hydrogenation of Unfunctionalized Multisubstituted Alkenes. ACS Sustainable Chem. Eng. 2022, 10, 1078-1082; (e) Sunada, Y.; Ogushi, H.; Yamamoto, T.; Uto, S.; Sawano, M.; Tahara, A.; Tanaka, H.; Shiota, Y.; Yoshizawa, K.; Nagashima, H. Disilaruthena- and Ferracyclic Complexes Containing Isocyanide Ligands as Effective Catalysts for Hydrogenation of Unfunctionalized Sterically Hindered Alkenes. J. Am. Chem. Soc. 2018, 140, 4119-4134; (f) Tahara, A.; Tanaka, H.; Sunada, Y.; Shiota, Y.; Yoshizawa, K.; Nagashima, H. Theoretical Study of the Catalytic Hydrogenation of Alkenes by a Disilafer-racyclic Complex: Can the Fe-Si σ-Bond-Assisted Activation of H-H Bonds Allow Development of a Catalysis of Iron? J. Org. Chem. 2017, 81, 10900-10911; (g) Sunada, Y.; Tsutsumi, H.; Shigeta, K.; Yoshida, R.; Hashimoto, T.; Nagashima, H. Catalyst design for iron-promoted reductions: an iron disilyl-dicarbonyl complex bearing weakly coordinating η²-(H-Si) moieties. Dalton Trans. 2013, 42, 16687-16692.

[10] Ito, T.; Sunada, Y. A Cobalt-Containing Polysilane as an Effective Solid-State Catalyst for the Hydrosilylation of Alkenes. Org. Process Res. Dev. 2023, 27, 1203–1209.

[11] Chen, X.; Liang, C. Transition metal silicides: fundamentals, preparation and catalytic applications. Catal. Sci. Technol. 2019, 9, 4785–4820.

[12] Lai, Q.; Zhang, X.; Jiang, S.; Krzyaniak, M. D.; Alayoglu, S.; Agarwal, A.; Liu, Y.; Edenfield, W. C.; Kobayashi, T.; Wang, Y.; Dravid, V.; Wasielewski, M. R.; Miller, J. T.; Kratish, Y.; Marks, T. J. Stable single-site organonickel catalyst preferentially hydrogenolyses branched polyolefin C–C bonds. Nat. Chem. 2025, 17, 1488–1496.

[13] (a) Grunthaner, P. J.; Grunthaner, F. J.; Madhukar, A.; Chemical bonding and charge redistribution: Valence band and core level correlations for the Ni/Si, Pd/Si, and Pt/Si systems Available. J. Vac. Sci. Technol. 1982, 20, 680-683; (b) Tam, P. L. Nyborg, L. Sputter deposition and XPS analysis of nickel silicide thin films. Surf. Coat. Technol. 2009, 203, 2886-2890.

[14] Stork, G. The Base Effect in Catalytic Hydrogenation. A Simple Synthesis of 6-Methoxy-α-tetralone. J. Am. Chem. Soc. 1947, 69, 576–579.

[15] Wiesenfeldt, M. P.; Nairoukh, Z.; Dalton, T.; Glorius, F. Selective Arene Hydrogenation for Direct Access to Saturated Carbo- and Heterocycles. Angew. Chem. Int. Ed. 2019, 58, 10460–10476.

[16] Yuan, T.; Gong, H.; Kailasam, K.; Zhao, Y.; Thomas, A.; Zhu, J. Controlling hydrogenation selectivity with Pd catalysts on carbon nitrides functionalized silica. J. Catal. 2015, 326, 38–42.

[17] (a) Entel, J.; Ruof, C. H.; Howard, H. C. Reactions of Benzofurans with Hydrogen. J. Am. Chem. Soc. 1951, 73, 4152-4158; (b) Wang, X.; Rinaldi, R. Exploiting H-transfer reactions with RANEY® Ni for upgrade of phenolic and aromatic biorefinery feeds under unusual, low-severity conditions. Energy Environ. Sci. 2012, 5, 8244-8260.

[18] Yao, H. C.; Emmett, P. H. Kinetics of Liquid Phase Hydrogenation. IV. Hydrogenation of Nitrocompounds Over Raney Nickel and Nickel Powder Catalysts. J. Am. Chem. Soc. 1962, 84, 1086–1091.

Rights & permissions

2026 The Author(s). Chinese Journal of Chemistry published by SIOC, CAS, Shanghai and Wiley-VCH GmbH