Hydrogen-Transfer Catalysis with Pincer-Aryl Ruthenium (II) Complexes
Paulo Dani, Thomas Karlen, Robert A. Gossage, Serafino Gladiali and Gerard van Koten*
*Debey Institute, Departement of Metal-Mediated Synthesis, Utrecht
University, Padualaan 8, 3584 CH Utrecht (The Netherlands), Email:
g.vankoten
chem.uu.nl
P. Dani, T. Karlen, R. A. Gossage, S. Gladiali, G. van Koten, Angew. Chem. Int. Ed., 2000, 39, 743-745.
DOI: 10.1002/(SICI)1521-3773(20000218)39:4<743::AID-ANIE743>3.0.CO;2-I
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Abstract
Pincer-aryl ruthenium(II) complexes form active catalysts in the reduction of ketones by hydrogen transfer in iPrOH using KOH as promoter. At a KOH/Ru molar ratio of 20/1 only trace amounts of aldol products are formed. Under these conditions, the σ Ru-C bond is stable and the [Ru(PCP)PPh3] fragment is preserved.
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Details
The document discusses the synthesis and characterization of pincer-aryl ruthenium(II) complexes and their application in hydrogen-transfer catalysis. These complexes, containing stable metal-carbon sigma bonds, are effective in various metal-mediated organic transformations, including the reduction of ketones to alcohols using isopropanol (iPrOH) as the hydrogen source and potassium hydroxide (KOH) as the promoter. The study highlights the high catalytic activity and turnover frequencies (TOF) of these complexes, particularly those with bis(phosphanyl)aryl (PCP) ligands, which outperform traditional ruthenium(II) complexes with monodentate phosphane ligands. The research also identifies a ruthenium hydrido species as the likely active catalyst in the hydrogen-transfer process. Additionally, the document briefly mentions the synthesis of an open-framework antimony(III) phosphate, which incorporates fluorine and features a complex network of pseudo-octahedral and pseudo-trigonal-bipyramidal units. This material was synthesized using a structure-directing agent under hydrothermal conditions and is part of ongoing research into open-framework materials with potential applications in catalysis, separations, and ion exchange. The work is supported by various scientific organizations and highlights the collaborative efforts in advancing the field of organometallic chemistry and material science
Key Words
homogeneous catalysis, hydrido complexes, hydrogen transfer, Meerwein-Ponndorf-Verley Reduction, reductions, ruthenium, isopropanol
ID: J06-Y2000-530
