Chelation-assisted activation of C-X bonds (X = Cl, Br, and I) took place in the reaction of [Rh(PPh3)(2)(acetone)(2)](+) and 2-(2-halophenyl)pyridine or 10-halobenzo[h]quinoline. A series of 16-electron five-coordinate cationic rhodium(III) monohalide complexes was synthesized at room temperature. Neutral octahedral rhodium(III) dihalide complexes were obtained when the corresponding cationic monohalide complexes were further heated in acetone. Rhodium and iridium diiodides with these cyclometalation motifs could be alternatively synthesized from the reaction of the corresponding cyclometalated hydride complexes and I-2. X-ray crystal structures of representative monohalide and dihalide complexes are reported, Octahedral rhodium(III) dihalide complexes are active catalysts for the dimerization of terminal alkynes, while 16-electron cationic rhodium(III) monohalides are inactive.