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Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/217084
Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes
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Enantiopure P-stereogenic methylphosphane-boranes (SP)-P(BH3)PhArMe (ArMe; Ar = 1-naphthyl (NpMe), and 2-biphenylyl (BiphMe)) have been used to prepare diphosphanes of the type ArPhPCH2PR2 (R = Ph, iPr or tBu; ArR). The ligands have been reacted with [Rh(COD)2]BF4 to furnish the corresponding six monochelated [Rh(COD)(ArR)]BF4 organometallic compounds (RhArR) or, depending on the reaction conditions, the bis(chelated) coordination compound [Rh(BiphiPr)2]BF4 as a mixture of cis and trans isomers. The crystal structure of cis-[Rh(BiphiPr)2]BF4 was obtained. The coordination of the BiphR with [RuCl(μ-Cl)(η6-p-cymene)2]2 under different conditions produced cationic chelated complexes of the type [RuCl(η6-p-cymene)(κ2-BiphR)]PF6 (RuBiphR) and the neutral monocoordinated complex [RuCl2(η6- p-cymene)(κ1-BiphPh)] (RuBiphPh') with the uncoordinated P-stereogenic moiety. The Rh(I) complexes were used in the catalytic hydrogenation of functionalized olefins and the Ru(II) complexes were tested in the transfer hydrogenation of acetophenone. Both precursors displayed good activities with moderate enantioselectivities.
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EUSAMIO, Javier, MEDINA, Yaiza m., CÓRDOBA, Javier c., VIDAL FERRAN, Anton, SAINZ GARCÍA, Daniel, GUTIÉRREZ, Albert, FONT BARDIA, Ma. mercedes, GRABULOSA, Arnald. Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes. _Dalton Transactions_. 2023. Vol. 52, núm. 2424-2439. [consulta: 26 de febrer de 2026]. ISSN: 1477-9226. [Disponible a: https://hdl.handle.net/2445/217084]