Synthesis, Structural Analysis, and Catalytic Properties of Tetrakis(binaphthyl or octahydrobinaphthyl phosphate) Dirhodium(II,II) Complexes

The X-ray structural analyses of homoleptic Rh­(II) complexes made of enantiopure (<i>R</i>)-1,1′-binaphthyl and (<i>R</i>)-(5,5′,6,6′,7,7′,8,8′-octahydro)­binaphthyl phosphate ligands are for the first time presented. The possibility to introduce halogen atoms at the 3,3′-positions is also reported. The isolated dirhodium complexes were further tested as catalysts (1 mol %) in enantioselective cyclopropanations and Si–H insertion reactions, affording chiral cyclopropanes and silanes in good yield but moderate enantioselectivity (ee max 63%)

Secondary Phosphine Oxide–Gold(I) Complexes and Their First Application in Catalysis

A series of new secondary phosphine oxide (SPO)–gold­(I) complexes have been synthesized and characterized by X-ray crystallography. Complexes exhibited dimeric structures interconnected by O–H···Cl hydrogen bonds. Their first use in homogeneous catalysis is reported and suggests a broad field of application in prototypical enyne cycloisomerization and hydroxy- and methoxycyclization reactions