The formation of heteroligated Rh-1 complexes containing two different hemilabile phosphinoallcyl ligands, (kappa(2)-Ph2PCH2CH2S-Ary1)(kappa(1)-Ph2PCH2CH2O-C6H5)RhCl, through a halide-induced ligand rearrangement (HLLR) reaction has been studied mechanistically. The half-life of this rearrangement reaction depends heavily on the Rh-1 precursor used and the chelating ability of the phosphinoallcyl thioether (PS) ligand, while the chelating ability of the phosphinoalkyl ether (PO) ligand has less of an effect. An intermediate complex which contains two PO ligands, (nbd)(kappa(1)-Ph2PCH2CH2O-C6H5)(2)RhCl (nbd = norbornadiene), converts to (nbd)(kappa(1)-Ph2PCH2CH2O-C6H5)RhCl resulting in a free PO ligand. The free PO ligand can then react with a homoligated PS complex [(kappa(2)-Ph2PCH2CH2S-Aryl)(2)Rh]Cl-+(-) producing the heteroligated product. The PS ligand generated during the reaction pathway can be trapped by the monoligated PO complex (nbd)(kappa(1)-Ph2PCH2CH2O-C6H5)RhCl, leading to the formation of the same heteroligated product. In this study, some of the key intermediates and reaction steps underlying the HILR reaction have been identified by variable temperature P-31{H-1} NMR spectroscopy and in two cases by single-crystal X-ray diffraction studies. Significantly, this work provides mechanistic insight into the HILR process, which is a key reaction used to prepare a large class of highly sophisticated three-dimensional metallosuprarnolecular architectures and allosteric catalysts.