Rhodium(III)-mediated cycloaddition reactions of alkynes

Heating [Cp＊Rh(η²-NO₃)(OTf) (1) and PhC≡CPh in EtOH for 3 h gave a η⁴-cyclobutadienerhodium complex, [Cp＊Rh(η⁴-C₄Ph₄)] (2). Complex 1 reacted with HC=CPh in acetone at room temperature for 3 h to give a (η⁴-cyclobutadiene)-rhodium complex, [Cp＊Rh(η⁴-C₄HPhC=CPh)] (3). Whereas, the reactions of 1 with HC=CCH₂Cl in acetone at room temperature for 3 h gave the triply halide-bridged dinuclear rhodium complex, [Cp＊Rh(μ₂-Cl)₃RhCp＊](OTf) (4). Complexes 2-4 have been structurally characterized by X-ray diffraction.