The pyrolysis of toluene, the simplest methyl-substituted aromatic molecule, has been studied behind reflected shock waves using a single pulse shock tube. Experiments were performed at nominal high pressures of 27 and 45 bar and spanning a wide temperature range from 1200 to 1900 K. A variety of stable species, ranging from small hydrocarbons to single ring aromatics ( principal soot precursors such as phenylacetylene and indene) were sampled from the shock tube and analyzed using standard gas chromatographic techniques. A detailed chemical kinetic model with 262 reactions and 87 species was assembled to simulate the stable species profiles ( specifically toluene, benzene and methane) from the current high-pressure pyrolysis data sets and shock tube-atomic resonance absorption spectrometry (ARAS) H atom profiles obtained from prior toluene pyrolysis experiments performed under similar high-temperature conditions and lower pressures from 1.5 to 8 bar. The primary steps in toluene pyrolysis represent the most sensitive and dominant reactions in the model. Consequently, in the absence of unambiguous direct experimental measurements, we have utilized recent high level theoretical estimates of the barrierless association rate coefficients for these primary reactions, C6H5 + CH3 -> C6H5CH3 (1a) and C6H5CH2 + H -> C6H5CH3 (1b) in the detailed chemical kinetic model. The available data sets can be successfully reconciled with revised values for Delta H-f(298K)0(C6H5CH2) = 51.5 +/-1.0 kcal/mol and Delta H-f(298K)0(C6H5) = 78.6 +/- 1.0 kcal/mol that translate to primary dissociation rate constants, reverse of 1a and 1b, represented by k(-1a,infinity) (4.62 x 10(25)) T(-2.53)exp[-104.5 x 10(3)/RT] s(-1) and k(-1b,infinity)) (1.524 x 10(16)) T(-0.04)exp[-93.5 x 10(3)/RT]s(-1) (R in units of cal/(mol K)). These high-pressure limiting rate constants suggest high-temperature branching ratios for the primary steps that vary from 0.39 to 0.52 over the temperature range 1200-1800 K.