The nascent vibrational and the near-nascent rotational state distributions for the SO(X-3 Sigma(-)) product following the oxidation reaction of thiophosgene (CSCl2) with O(P-3) have been studied by laser-induced fluorescence (LIF) spectroscopy on the (B-3 Sigma(-)-X-3 Sigma(-)) transition. O(P-3) atoms are produced from the 355 nm photodissociation of NO2. The measured SO(X-3 Sigma(-)) product vibrational state distribution can be characterized as Boltzmann with a vibrational temperature T-vib = 1150 +/- 55 K corresponding to 8% of the available energy for the reaction. The statistical nature of the SO(X-3 Sigma(-)) vibrational state distribution suggests a stable intermediate for this reaction, and ab initio calculations confirm a triplet dichlorosulfine (Cl2CSO((3)A '')) as a minimum on the excited triplet state potential energy surface. Statistical modeling of the observed SO(X-3 Sigma(-)) vibrational state distribution results in an available energy E = 18 kcal/mol, which is 1.6 kcal/mol more than the exoergicity of this reaction. On the basis of ab initio calculations in conjunction with the analysis of the experimental data in light of the statistical model, we propose little or no barrier in excess of the endothermicity for the fragmentation of the Cl2CSO((3)A '') intermediate at the exit channel. The near-nascent rotational state distribution of SO(X-3 Sigma(-), v '' = 0) can be characterized by a rotational temperature T-R = 537 +/- 35 K corresponding to 6.7% of the available energy for the reaction. This small fraction of energy partitioned into SO(X-3 Sigma(-)) rotations may arise from a correlation between the SO rotations and the CSO bend in the Cl-2-CSO((3)A '') complex at the exit channel.