Accessing Monosubstituted Cyclopentadienyl Rhodium(I) and Iridium(I) Complexes by a Simultaneous Nucleophilic Addition-Metalation Approach to Fulvenes

Despite advances in the synthesis of polysubstituted cyclopentadienyl metal complexes, the rapid access to a library of monosubstituted Cp bearing metal complexes remains challenging. A convenient and general method to access a broad range of monosubstituted cyclopentadienyl rhodium(I) and iridium(I) complexes is reported. The process involves a direct nucleo-metalation of fulvenes with widely available metal precursors, affording a set of CpRhI(olefin)(2) and CpIrI(olefin)(2) complexes in high yields. A broad range of oxygen-, nitrogen-, and carbon-based nucleophiles were found competent for the process and offer good tuning abilities of the cyclopentadienyl portion.