Synthesis of [RhCl(CO)(cyclopentadienone)]2 from [RhCl(cod)]2 and a 1,6-diyne under CO: application to Rh(I)-catalyzed tandem [2+2+1] carbonylative cycloaddition of diynes and Claisen rearrangement.

Although Rh(I)Cl(CO)(cpd) (cpd = cyclopentadienone) complexes were identified more than 40 years ago, their exact structures have not been determined because of the polymeric nature of these complexes. We determined the structure of [Rh(I)Cl(CO)(cpd)](2), which was formed by the reaction of [Rh(cod)Cl](2) with a 1,6-diyne under CO. In addition, based on determination of the structure of the [Rh(I)Cl(CO)(cpd)](2) complex, we identified a new catalytic tandem reaction--the Rh-catalyzed [2+2+1] carbonylative cycloaddition of phenoxide-substituted diynes and Claisen rearrangement.