The ultrafast reaction dynamics following 295-nm photodissociation of Re-2(CO)(10) were studied experimentally with 300-fs time resolution in the reactive, strongly coordinating CCl4? solution and in the inert. weakly coordinating hexane solution. Density-functional theoretical (DFT) and ab initio calculations were used to further characterize the transient intermediates seen in the experiments. It was found that the quantum yield of the Re-Re bond dissociation is governed by geminate recombination on two time scales in CCl4, similar to 50 and similar to 500 ps. The recombination dynamics are discussed in terms of solvent caging in which the geminate Re(CO)(5) pair has a low probability to escape the first solvent shell in the first few picoseconds after femtosecond photolysis. The other photofragmentation channel resulted in the equatorially solvated dirhenium nonacarbonyl eq-Re-2(CO)(9)(solvent). Theoretical calculations indicated that a structural reorganization energy cost on the order of 6-7 kcal/mol might be required for the unsolvated nonacarbonyl to coordinate to a solvent molecule. These results suggest that for Re(CO)(5) the solvent can be treated as a viscous continuum, whereas for the Re-2(CO)(9) the solvent is best described in molecular terms.