Synthesis of Functionalized (η 5 ‐Indenyl)rhodium(III) Complexes and Their Application to C−H Bond Functionalization

It has been established that reductive complexation of functionalized benzofulvenes, which are readily prepared from commercially available indene and 2‐methylindene, with RhCl 3 in ethanol affords the corresponding indenyl–rhodium(III) dichlorides bearing substituents at the 1‐ (H or CO 2 Et), 2‐ (H or Me), and 3‐ [CH 2 Ph or CH 2 (2‐MeOC 6 H 4 )] positions. The indenyl–rhodium(III) complexes bearing one ethoxycarbonyl group showed higher thermal stability and regioselectivity than our previously reported Cp E Rh III complex toward the oxidative [3+2] annulation of acetanilides with internal alkynes.