Equilibration occurs among the species MeReO(dithiolate)Py, MeReO(dithiolate)(PZ₃), Py, and PZ₃ where the chelating dithiolate ligand is 1,2-ethanedithiol (edt) or 1,3-propanedithiol (pdt), Py stands for NC₅H₄-4-X and PZ₃ for both P(C₆H₄-4-Y)₃ and P(alkyl)_n(Ph)_3−n. Equilibrium constants in the pdt series were evaluated directly; values of K generally favor phosphane coordination and range from 4.8 × 10⁻² (X = NMe₂, Y = Cl) to 3.2 × 10⁴ (X = CN, Y = OMe). The values of K are well correlated by the Hammett equation with ρ_X^K = 2.7(3) and ρ_Y^K = −2.0(3). Kinetic data were determined with the stopped-flow method for 65 reactions of the edt and pdt complexes, and resolved into forward and reverse components by use of the equilibrium constants. Values of k_for deviate markedly from Hammett behavior, especially along any series with a given X substituent, where plots of log k_for against 3σ_Y take on a V-shaped appearance. This pattern has been interpreted in terms of a two step mechanism for ligand substitution reactions of these complexes. The rate constants for those phosphanes that are the better Lewis bases are governed by Re–P bond formation. The rate constants for those phosphanes that are weaker Lewis bases, on the other hand, are governed by the second step in which an initial ψ-octahedral complex rotates towards a transition state that is an approximate trigonal prism. In so doing, the prior Re–P interaction is weakened, which gives rise to an increase in log k_for with σ_Y.