The reactions of either (PNP)Rh(Me)(Cl) or (PNP)Rh(H)(Cl) and some sulfur ligands L (L = SⁱPr₂, S^sBu₂, SⁿBu₂, SPhMe, SPh_2, SPh₂(=O), S^tBuMe, S^tBu_2, thiophene (T), benzothiophene (BT), dibenzothiophene (DBT)) produce the stable sulfur-bound complexes (PNP)Rh(L). Equilibrium constants Keq for the ligand exchange reaction (1) increase in the following order: S^tBu₂ < S^sBu₂ < (T, S^tBuMe) < SⁱPr₂ < BT < SPh₂ < DBT < SPhMe < SⁿBu₂ < SPh₂(=O).

The (PNP)Rh^I rhodium fragment generated by ligand dissociation from (PNP)Rh(SⁱPr₂) is capable of oxidative addition (2) of aromatic C-I, C-Br, C-Cl and Si-I, Si-Br, Si-Cl, Si-H bonds to yield to the family of complexes of general formula (PNP)Rh(X)(C₆H₅) and the unknown family of complexes (PNP)Rh(X)(SiMe_nCl_m), respectively. A detailed examination of the mechanism of the oxidative addition of aromatic C-I, C-Br and C-Cl will also be presented.