Towards Rhodium and Iridium Complexes Containing the Secondary Phosphane Ligand t Bu 2 PH

The reactions of [{M(μ‐Cl)(η 4 ‐cod)} 2 ] (M = Rh, 1a ; M = Ir, 1b ; cod = 1,5‐cyclooctadiene) and [Rh(acac)(olefin) 2 ] (acac = acetylacetonate; olefin = ethene, 3a ; olefin = cis ‐cyclooctene = coe, 3b ) with t Bu 2 PH in dichloromethane at room temperature were investigated, and the compounds [MCl( t Bu 2 PH)(η 4 ‐cod)] (M = Rh, 2a ; M = Ir, 2b ) as well as [Rh(acac)( t Bu 2 PH) 2 ] ( 4 ) were obtained in good yields. Furthermore, a one‐pot synthesis of trans ‐[IrCl(C 2 H 4 )( t Bu 2 PH) 2 ] ( 6b ) starting from [{Ir(μ‐Cl)(coe) 2 } 2 ] ( 5 ), ethene and t Bu 2 PH is described. All novel complexes were characterized using spectroscopic methods and the molecular structures of 2b , 6b , and trans ‐[RhCl(C 2 H 4 )( t Bu 2 PH) 2 ] ( 6a ) determined using X‐ray crystallography.