Rhodium and ruthenium complexes of methylene-bridged, P-stereogenic, unsymmetrical diphosphanes. Issue 8 (31st January 2023)

• Record Type: Journal Article
• Authors: Eusamio, Javier; Medina, Yaiza M.; Córdoba, Javier C.; Vidal-Ferran, Anton; Sainz, Daniel; Gutiérrez, Albert; Font-Bardia, Mercè; Grabulosa, Arnald
• Is Part Of: Dalton transactions. Volume 52:Issue 8(2023)
• Page Start: 2424
• Page End: 2439
• Publication Date: 2023-01-31
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt04026c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : P -stereogenic, methylene-bridged unsymmetrical diphosphanes coordinate to Rh(i ) and Ru(ii ), forming different complexes. The complexes are active in catalytic reductions. Abstract : Enantiopure P -stereogenic methylphosphane-boranes ( S P )-P(BH3 )PhArMe (ArMe ; Ar = 1-naphthyl (NpMe ), and 2-biphenylyl (BiphMe )) have been used to prepare diphosphanes of the type ArPhPCH2 PR2 (R = Ph, iPr or t Bu; 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)(η 6 - p -cymene)2 ]2 under different conditions produced cationic chelated complexes of the type [RuCl(η 6 - p -cymene)(κ 2 -BiphR )]PF6 (RuBiphR ) and the neutral monocoordinated complex [RuCl2 (η 6 - p -cymene)(κ 1 -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.