Homogeneous catalysis in multiphase liquid systems  Page description

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Details of project

  
Identifier
43365
Type K
Principal investigator Joó, Ferenc
Title in Hungarian Homogén katalízis többfázisú folyadékrendszerekben
Title in English Homogeneous catalysis in multiphase liquid systems
Panel Chemistry 1
Department or equivalent Department of Physical Chemistry (University of Debrecen)
Participants Bényei, Attila Csaba
Horváth, Henrietta
Kathó, Ágnes
Papp, Gábor
Starting date 2003-01-01
Closing date 2007-12-31
Funding (in million HUF) 15.743
FTE (full time equivalent) 0.00
state closed project





 

Final report

  
Results in Hungarian
Megvalósítottuk CaCO3 és MgCO3 homogénkatalitikus hidrogénezését, vizes közegben CO2/H2 atmoszférában. Felismertük, hogy a Rh(I) és Ru(II) vízoldható foszfinkomplexei jó hatásfokkal katalizálják a H2/D2O és a D2/H2O közötti H-D izotópcserét. Alkinek kétfázisú szelektív hidrogénezését valósítottuk meg Ru(II) vízoldható foszfinkomplexeivel és megállapítottuk, hogy a diszubsztituált alkinek hidrogénezésének sztereoszelektivitása erősen függ a vizes fázis pH-jától. Elsők között állítottunk elő N-heterociklusos karbén ligandumú, vízoldható Rh(I)- és Ru(II)-komplexeket, melyek katalizálják alkének, aldehidek és ketonok hidrogénezését tovább allil-alkoholok redox izomerizációját a megfelelő ketonná ill. aldehiddé. Számos esetben kimutattuk, hogy vizes közegben a foszfin vagy karbén ligandumú kloro-komplexek klorid disszociációt szenvednek, ami kationos komplexek spontán képződéséhez és ezzel a katalitikus sajátságok megváltozásához vezet. Lipid membránok homogénkatalitikus hidrogénezésében megállapítottuk az egyedi lipidek reaktivitását. Kvantumkémiai számításokat végeztünk a vizes közeg hatásának leírására a fémorganikus katalízisben és megállapítottuk, hogy legalább három H2O molekulából álló klasztert kell tekinteni amikor a víz koordinációját vizsgáljuk. A katalitikusan aktív fémkomplexeket szilárd hordozóra rögzítettük és sikeresen alkalmaztuk alkének, alkinek, aldehidek, szteroidok szelektív hidrogénezésében mind szuszpenzióban, mind áramlásos mikroreaktorban.
Results in English
A method was developed for the homogeneous catalytic hydrogenation of CaCO3 and MgCO3 in aqueous media under a H2/CO2 atmosphere. It was established that water-soluble phosphine complexes of Rh(I) and Ru(II) efficiently catalyze the H/D exchange in H2/D2O and D2/H2O. Alkynes were selectively hydrogenated in aqueous organic biphasic systems with water-soluble Ru(II)-phosphine catalysts, where the stereoselectivity of the hydrogenation of disubstituted alkynes is strongly pH-dependent. Hitherto uknown water-soluble N-heterocyclic carbene complexes of Rh(I) and Ru(II) were synthetized and applied for the catalysis of hydrogenation of alkenes, alkynes, aldehydes and ketones, as well as for the redox isomerization of allylic alcohols. It was found in several cases, that in aqueous solution chloride-containing phosphine or carbene complexes undergo chloride dissociation with the spontaneous formation of cationic complexes. The individual reactivities of the constituent lipids in the hydrogenation of liposomes were established. Quantum chemical calculations were performed to study the effect of water in aqueous organometallic catalysis and it was established that clusters of at least three H2O molecules should be considered when modelling the coordination of water. The catalytically active metal complexes were heterogenized on solid supports and succesfully used for selective hydrogenations of alkynes, aldehydes and steroids both in suspension and in a microfluidic flow reactor.
Full text http://real.mtak.hu/1038/
Decision
Yes





 

List of publications

  
Kovács G; Nádasdi L; Laurenczy G; Joó F: Aqueous organometallic catalysis. Isotope exchange reactions in H2-D2O and D2-H2O systems catalyzed by water-soluble Rh- and Ru-phosphine complexes., Green Chem 5: 213-217, 2003
Csabai P; Joó F: Reactivity of the individual lipid classes in homogeneous catalytic hydrogenation of model and biomembranes detected by MALDI-TOF mass spectrometry, Catal Commun 4: 275-280, 2003
Horváth H; Laurenczy G; Kathó Á: Water-soluble (arene)ruthenium(II)-phosphine complexes and their catalytic activity in the hydrogenation of bicarbonate in aqueous solution., J Organometal Chem 689: 1036-1045, 2004
Jessop PG; Joó F; Tai C-C.: Recent Advances in the Homogeneous Hydrogenation of Carbon Dioxide, Coord Chem Rev 248: 2425-2442, 2004
Kovács J; Joó F; Bényei AC; Laurenczy G: Reactions of [Ru(H2O)6]2+ with water-soluble tertiary phosphines, Dalton Trans 2336-2340, 2004
Csabai P; Joó F: Synthesis and Catalytic Properties of New Water-Soluble Ruthenium(II)-N-Heterocyclic Carbene Complexes, Organometallics 23: 5640-5643, 2004
Jószai I; Joó F: Hydrogenation of aqueous mixtures of calcium carbonate and carbon dioxide using a water-soluble rhodium(I)-tertiary phosphine complex catalyst, J Mol Catal A: Chemical 224: 87-91, 2004
Elek J; Mangelings D; Joó F; Heyden YV: Chemometric modelling of the catalytic hydrogenation of bicarbonate to formate in aqueous media, React Kinet Catal Lett 83: 321-328, 2004
Joó F, Kathó Á: Hydrogenation, In: Cornils B, Herrmann WA (ed.) Aqueous-Phase Organometallic Catalysis, Weinheim, Wiley-VCH, 2004. pp 429-463, 2004
Kovács G; Ujaque G; Lledós A; Joó F: The role of water in the stereoselective hydrogenation of 1,2-diphenylacetylene catalyzed by the water-soluble [{RuCl2(mtppms)2}2]. A theoretical study., Eur. J. Inorg. Chem. [közlésre beküldve], 2007
Joó F: Water. The greenest solvent for organometallic catalysis?, 8th Eurasia Conference on Chemical Sciences, Hanoi (Vietnam), 2003. Book of Abstracts, p. 457, 2003
Joó F; Jószai I; Papp G; Kathó Á: Catalytic hydrogenations in aqueous systems with transition metal tertiary phosphine complex catalysts, 226th Annual Meeting of the American Chemical Society, New York, NY, 2003. Book of Abstracts, INOR-308, 2003
Zsigmond Á; Undrala S; Notheisz F; Papp G; Joó F: New applications of anchored Ru(II)-N-heterocyclic carbene complexes, Catal. Lett. [közlésre elfogadva], 2007
Kathó Á; Molnár J; Papp G; Joó F: Effect of NaI on the aqueous/organic biphasic hydrogenation of cinnamaldehyde catalyzed by [{RuCl2(TPPMS)2}2], ISHC-14 Munich, 2004. Book of Abstracts, p. 217, 2004
Horváth H; Papp G; Joó F; Kathó Á: Comparison of the catalytic properties of the easily interconvertible, water-soluble [RuH(CO)(H2O)(mtppms)3]+, ISHC-14 Munich,2004. Book of Abstracts, p. 313, 2004
Horváth HH; Papp G; Csajági Cs; Joó F: Selective catalytic hydrogenations in a microfluidics-based high throughput flow reactor on ion-exchange supported transition metal complexes. A modular approach to the heterogenization of soluble complex catalysts, Catal. Commun. 8: 442-446, 2007
Joó F: Green Chemistry through Aqueous Organometallic Catalysis, Int. Conf. on Knowledge-based Materials and Technologies for Sustainable Chemistry (Tallinn, Estonia, 2005), p.65, 2005
Horváth H; Papp G; Kathó Á; Joó F: Metamorphosis of the [RuHCl(CO)(mtppms)3] catalyst during the hydrosilylation of alkynes in aqueous-organic biphasic systems., Int. Conf. on Knowledge-based Materials and Technologies for Sustainable Chemistry (Tallinn, Estonia), p. 56, 2005
Horváth HH; Joó F: Stereoselective homogeneous catalytic hydrogenation of disubstituted alkynes in aqueous-organic biphasic media, React. Kinet. Catal. Lett., 85, 355-360, 2005
Kovács G; Schubert G; Joó F; Pápai I: Theoretical Mechanistic Study of Rhodium(I) Phosphine-Catalyzed H/D Exchange Processes in Aqueous Solutions, Organometallics, 24, 3059-3065, 2005
Papp G; Horváth H; Kathó Á; Joó F: Aqueous Organometallic Chemistry. Synthesis and Solution Equilibria of Carbonylchlorotris[3-(diphenylphosphino)benzenesulfonato]-hydridoruthenate(3-), Helvetica Chimica Acta, 88, 566-573, 2005
Kovács J; Joó F; Frohning CD: Anion effects in the formation of the active catalyst in the Ruhrchemie-Rhőne Poulenc aqueous biphasic hydroformylation process. Are there any?, Canadian J. Chem., 83, 1033-1036, 2005
Kovács G; Ujaque G; Lledós A; Joó F: Theoretical investigation of the selective C=C hydrogenation of unsaturated aldehydes catalyzed by [{RuCl2(mtppms)2}2] in acidic media., Organometallics 25: 862-872, 2006
Kovács G; Schubert G; Joó F; Pápai I: Theoretical investigation of catalytic HCO3- hydrogenation in aqueous solutions., Catalysis Today 115: 53-60, 2006
F. Joó, Á. Kathó: Hydrogenation, In Multiphase Homogeneous Catalysis (B Cornils, WA Herrmann, IT Horváth, W Leitner, S Mecking, H Olivier-Bourbigou, D Vogt, eds.) Wiley-VCH, Weinheim, pp. 187-196, 2005
Joó F; Kathó Á: Two-phase aqueous hydrogenations, In Handbook of Homogeneous Hydrogenation (J. G. de Vries, C. Elsevier, eds.), Wiley-VCH, Weinheim, pp. 1327-1359, 2006
Zsigmond Á; Madácsi R; Notheisz F; Mernyák E; Joó F: Selective hydrogenations of steroids catalyzed by heterogenized Ru complexes., React. Kinet. Catal. Lett. 87: 297-304, 2006
Jószai R; Beszeda I; Bényei AC; Fischer A; Kovács M; Maliarik M; Nagy P; Schukarev A; Tóth I: Metal-metal bond or isolated metal centers? Interaction of Hg(CN)2 with Square Planar Transition Metal Cyanides, Inorg. Chem. 44, 9643-9651, 2005
Kathó Á; Fekete M; Papp G; Laurenczy G; Joó F: Biphasic Organometallic Catalysis with Water-Soluble Ruthenium(II) Complexes., Chimia 59, 678, 2005
Kovács J; Joó F: pH-Dependent catalytic reactions of allylic alcohol by Rh(I) complexes in aqueous media, 16th FECHEM Conf. Organometal. Chem. (Budapest, Hungary, 2005), Book of Abstracts, p. 125, 2005
Fekete M; Joó F: Redox isomerization of allylic alcohols in aqueous-organic biphasic system catalyzed by water-soluble Ru(II)-N-heterocyclic carbene complexes, Catal. Commun 7: 783-786, 2006
Rossin A; Kovács G; Ujaque G; Lledós A; Joó F: The active role of the water solvent in the regioselective C=O hydrogenation of unsaturated aldehydes in basic media, Organometallics 25: 5010-5023, 2006
Joó F; Horváth HH; Papp G: Hydrogenations on supported Ru(II)- and Rh(I)-complex catalyst using the H-CubeTM reactor., 1st Int. Microfluidic-Based Hydrogenation Course, Thales Nanotechnology Inc. (Budapest, Hungary, September 8, 2005), 2005
Csabai P; Joó F; Trzeciak AM, Ziólkowski JJ: Catalytic activity of half-sandwich Ru(II)-N-heterocyclic carbene complexes in the oligomerization of alkynes, J. Organometal. Chem. 691: 3371-3376, 2006
Zsigmond Á; Balatoni I; Bogár K; Notheisz F; Joó F: Selective hydrogenations on heterogenized ruthenium complexes., J. Catal. 227: 417-424, 2004
Bényei AC; Rangits G; Kuik Á; Skoda-Földes R; Kollár L: Intramolecular Hydrogen Bonds in Heterodisubstituted Ferrocene Diamides, Abstr. 23rd Eur. Crystallographic Meeting, Leuven, p. 247, 2007
Balogh J; Zsoldos-Mády V; Frigyes D; Bényei AC; Skoda-Földes R; Sohár P: Synthesis of novel ferrocene labelled steroidal derivatives via palladium-catalysed carbonylation. X-ray structure of 17-(N-(4’-((2-ferrocenyl-ethenyl)-carbonyl)-phenyl)carbamoyl 5α-androst-16-ene, J. Organometal. Chem 692: 1614-1618, 2007
Tircsó Gy; Bényei AC; Király R; Lázár I; Pál R; Brücher E: Complexation properties of the di-, tri- and tetraacetate derivatives of bis-aminomethyl-phosphinic acid, Eur. J. Inorg. Chem. : 701-713, 2007
Tircsó Gy; Bényei AC; Brücher E; Kis A; Király R: Equilibria and structure of the lanthanide(III)-2-hydroxy-1,3-diaminopropane-N,N,N ',N '-tetraacetate complexes: Formation of alkoxo-bridged dimers in solid state and solution, Inorg. Chem. 45: 4951-4962, 2006
Brito I; López-Rodrigez M; Bényei A; Szilágyi L: Crystal and molecular structures of diglycosyl disulfide derivatives, Carbohydrate Res. 341: 2967-2972, 2006
Bényei AC; Gulyás H; Ozawa Y; Kimura K; Toriumi K; Kégl T; Bakos J: X-ray structures of the tris(2,4-xylyl)phosphane and its trisulfonated derivative: Molecular architecture of a water-soluble sulfonated phosphane with propeller chirality, J. Organometal. Chem. (in press), 2007



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