HETEROGENEOUS CATALYSIS IN SUSTAINABLE GREEN SOLVENT: ALKENES HYDROGENATION WITH NEW SILICA IMMOBILIZED PALLADIUM COMPLEX CONTAINING S,O-CHELATING LIGAND

Pd(II) complex containing S,O-chelating ligand was immobilized on surface of the amine functionalized silica support in scCO2 media. Silica-based catalyst (SiO2-ThiophPd(II)) were characterized by IR, SEM, XRF, and BET analyses. The catalytic activity of the immobilized catalyst in hydrogenation reactions of alkenes has been compared with the homogeneous counterpart. SiO2-ThiophPd(II) catalyst showed good activity and reusability than homogeneous system. The best conversion in styrene hydrogenation was obtained with TOF value as 5871 h-1 at 370 K, 10 bar H2 and 1500 psi total pressure. Especially, while homogeneous counterpart has not activity in cyclohexene hydrogenation, it has been provided 100% cyclohexane conversion with the immobilized catalyst. It has also been found that the catalyst can be reused at least ten times without significant loss of activity in the styrene hydrogenation

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  • [1] Mehendale NC, Bezemer C, Walree CA Van, et al. Novel silica immobilized NCN-pincer palladium ( II ) and platinum ( II ) complexes : Application as Lewis acid catalysts. 2006; 257:167–175.
  • [2] Jessop PG, Heldebrant DJ. Green Biphasic Homogeneous Catalysis. ChemInform 2006; 37(35):627–648.
  • [3] Mäki-Arvela P, Hájek J, Salmi T, et al. Chemoselective hydrogenation of carbonyl compounds over heterogeneous catalysts. Appl Catal A Gen 2005; 292:1–49.
  • [4] Cornils B, Herrmann WA. Concepts in homogeneous catalysis : the industrial view. 2003; 216:23–31.
  • [5] Corma A, Garcia H. Silica-bound homogenous catalysts as recoverable and reusable catalysts in organic synthesis. Adv Synth Catal 2006; 348:1391–1412.
  • [6] Wang Z, Ding K, Uozumi Y. An Overview of Heterogeneous Asymmetric Catalysis. In: Handbook of Asymmetric Heterogeneous Catalysis. 2008; pp. 1–24.
  • [7] Merckle C, Blümel J. Improved Rhodium Hydrogenation Catalysts Immobilized on Oxidic Supports. Adv Synth Catal 2003; 34:5–15.
  • [8] Margelefsky EL, Zeidan RK, Davis ME. Cooperative catalysis by silica-supported organic functional groups. Chem Soc Rev 2008; 37:1118–1126.
  • [9] Jannes G. Supported homogeneous catalysts. Appl Catal 1985; 14(2):394.
  • [10] Thomas JM, Raja R. Catalytic significance of organometallic compounds immobilized on mesoporous silica: Economically and environmentally important examples. J Organomet Chem 2004; 689:4110–4124.
  • [11] Dioos BML, Vankelecom IFJ, Jacobs PA. Aspects of immobilisation of catalysts on polymeric supports. Adv Synth Catal 2006; 348:1413–1446.
  • [12] Hauthal WH. Advances with supercritical fluids [ review ]. Chemos 2001; 43:123–35.
  • [13] Sheldon RA. Green solvents for sustainable organic synthesis: state of the art. Green Chem 2005; 7:267–278.
  • [14] Mizuuchi H, Jaitely V, Murdan S, et al. Room temperature ionic liquids and their mixtures: Potential pharmaceutical solvents. Eur J Pharm Sci 2008; 33:326–31.
  • [15] Pozzi G, Cavazzini M, Cinato F, et al. Enantioselective catalysis in fluorinated media - Synthesis and properties of chiral perfluoroalkylated (salen)manganese complexes. European J Org Chem 1999; (8):1947–1955.
  • [16] Kankala RK, Zhang YS, Wang S, et al. Supercritical Fluid Technology : An Emphasis on Drug Delivery and Related Biomedical Applications. Adv Heal Mater 2017; 6:2–31.
  • [17] Budisa N, Schulze-makuch D. Supercritical Carbon Dioxide and Its Potential as a Life-Sustaining Solvent in a Planetary Environment. Life 2014; 4:331–340.
  • [18] Leitner W. Supercritical carbon dioxide as a green reaction medium for catalysis. Acc Chem Res 2002; 35(9):746–756.
  • [19] Rajagopalan B, Wei M, Musie GT, et al. Homogeneous catalytic epoxidation of organic substrates in CO2-expanded solvents in the presence of water-soluble oxidants and catalysts. Ind Eng Chem Res 2003; 42(25):6505–6510.
  • [20] Wang X, Kawanami H, Dapurkar SE, et al. Selective oxidation of alcohols to aldehydes and ketones over TiO2-supported gold nanoparticles in supercritical carbon dioxide with molecular oxygen. Appl Catal A Gen 2008; 349:86–90.
  • [21] Wu W, Li W, Han B, et al. Effect of organic cosolvents on the solubility of ionic liquids in supercritical CO2. J Chem Eng Data 2004; 49:1597–1601.
  • [22] Zhang X, Heinonen S, Levanen E. Applications of supercritical carbon dioxide in materials processing and synthesis. RSC Adv 2014; 4:61137–61152.
  • [23] Cooper BAI. Porous Materials and Supercritical Fluids. Adv Mater 2003; 15(13):1049–1059.
  • [24] Yilmaz F, Mutlu A, Unver H, et al. Hydrogenation of olefins catalyzed by Pd(II) complexes containing a perfluoroalkylated S,O-chelating ligand in supercritical CO2 and organic solvents. J Supercrit Fluids 2010; 54(2):202–209.
  • [25] Sharma RK, Mishra M, Sharma S, et al. Zinc ( II ) complex immobilized on amine functionalized silica gel : a novel , highly efficient and recyclable catalyst for multicomponent click synthesis of 1,4-disubstituted 1,2,3-triazoles. J Coord Chem Taylor & Francis 2016; 69:1152–1165.
  • [26] F Yilmaz, Y Karaağaç İK. Heterogenization of Homogeneous Perfluorothiophene Rh(I) Complex And Examination of Hydrogenation Activity in scCO2 Media. Anadolu Univ J Sci Technol A - Appl Sci Eng 2017.