Transient two-dimensional infrared (2DIR) spectroscopy is applied to the photodissociation of Mn-2(CO)(10) to 2 Mn(CO)(5) in cyclohexane Solution. By varying both the time delay between the 400 nm phototrigger and the 2DIR probe as well as the waiting time in the 2DIR pulse sequence, we directly determine the orientational relaxation of the vibrationally hot photoproduct. The orientational relaxation slows as the photoproduct cools, providing a measure of the transient temperature decay time of 70 +/- 16 ps. We compare the experimental results with molecular dynamics simulations and find near quantitative agreement for equilibrium orientational diffusion time constants but only qualitative agreement for nonequilibrium thermal relaxation. The simulation also shows that the experiment probes an unusual regime of thermal excitation, where the solute is heated while the solvent remains essentially at room temperature.