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Interactions of the (R) Ru-BINAP Catalytic Complex with an Inorganic Matrix in Stereoselective Hydrogenation of Methylacetoacetate – Kinetic, XPS and DRIFT Studies.
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SYSNO ASEP 0472520 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Interactions of the (R) Ru-BINAP Catalytic Complex with an Inorganic Matrix in Stereoselective Hydrogenation of Methylacetoacetate – Kinetic, XPS and DRIFT Studies. Author(s) Klusoň, Petr (UCHP-M) RID, ORCID, SAI
Krystyník, Pavel (UCHP-M) RID, SAI, ORCID
Dytrych, Pavel (UCHP-M) RID, ORCID, SAI
Bártek, L. (CH)Source Title Reaction Kinetics Mechanism and Catalysis. - : Springer - ISSN 1878-5190
Roč. 119, č. 2 (2016), s. 393-413Number of pages 21 s. Language eng - English Country NL - Netherlands Keywords (R)-Ru-BINAP complex ; stereoselective hydrogenation ; montmorillonite Subject RIV CC - Organic Chemistry R&D Projects GA15-14228S GA ČR - Czech Science Foundation (CSF) Institutional support UCHP-M - RVO:67985858 UT WOS 000388189000003 EID SCOPUS 84986244069 DOI 10.1007/s11144-016-1078-6 Annotation Stereoselective hydrogenation of methyl acetoacetate to optical isomers of methyl-3-hydroxybutanoate over various forms of supported [RuCl((R)-BINAP)(p-cymene)]Cl is reported. The catalysts were prepared via two alternative methods: direct immobilization, and surface anchorage with heteropolyacids. The kinetic data (rate constants, optical yields, overall selectivity to methyl-3-hydroxybutanoate) were discussed and interpreted with help of XPS and DRIFT to assess bonding surface interactions. In all cases montmorillonite as a model support was employed. It was shown that the stereoselective course was dependent on the mode of [RuCl((R)-BINAP)(p-cymene)]Cl immobilization. The procedure based on the commonly used impregnation did not provide a catalyst with a stable anchorage of the active complex. Strong surface anchorage was found for a catalystproduced with help of H4SiMo12O40 heteropolyacid, but due to structural changes upon the reaction the catalyst performance in the reaction was poor. When H3PW12O40 was employed, the immobilization provided a catalyst with a very good performance. The two-step immobilization via the dimer [RuCl2(p-cymene)](2) instead of the one-step with [RuCl((R)-BINAP)(p-cymene)]Cl yielded a catalyst with the performance parameters comparable to the homogeneous experiments with [RuCl((R)-BINAP)(p-cymene)]Cl dissolved in the reaction mixture. It was due to breaking up the original dimer structure and accomplishing the surface interaction through the adsorbed monomeric units. Workplace Institute of Chemical Process Fundamentals Contact Eva Jirsová, jirsova@icpf.cas.cz, Tel.: 220 390 227 Year of Publishing 2017
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