In agreement with the experimental results of Halpern on (PPh3)(2)Pt(CH3)H, B3LYP and CCSD(T) calculations on the model species (PH3)(2)Pt(CH3)H (1) find that reductive elimination of methane from this four-coordinate, Pt(II) complex proceeds without prior PH3 ligand loss. The foe energy of activation calculated for reductive elimination of methane from 1 is in good agreement with the value measured for (PPh3)(2)Pt(CH3)H. In contrast to the case for 1, we were unable to find a genuine pathway for direct reductive elimination of methane, without concomitant ligand loss, from (PH3)(2)Cl2Pt(CH3)H (13). This computational finding is in accord with the observation that reductive eliminations from six-coordinate, Pt(IV) complexes almost invariably take place via a pathway involving loss of a Ligand, prior to the seductive elimination step. PH3 ligand loss is found to lower the barrier to reductive elimination by slightly more in the Pt(TV) complexes than in the Pt(II) complexes. However, our calculations indicate that the difference between the preferred pathways for reductive elimination from 1 and 13 can be primarily attributed to a reduction in the enthalpic cost of PH, ligand loss from the six-coordinate, Pt(IV) complex (13), compared to the four-coordinate, Pt(II) complex (1).