The nature and rate of thermal transport through molecular junctions depend on the length over which thermalization occurs. For junctions formed by alkane chains, in which thermalization occurs only slowly, measurements reveal that thermal resistance is controlled by bonding with the substrates, whereas fluorination can introduce thermal resistance within the molecules themselves, although the mechanism remains unclear. Here we present results of quantum-mechanical calculations of elastic and inelastic scattering rates, the length over which thermalization occurs, and thermal conductance in alkane and perfluoroalkane junctions. The contribution to thermalization of quantum effects that give rise to many-body localization (MBL) in isolated molecules is examined. While MBL does not occur due to dephasing, thermalization is typically too slow to establish local temperature if the same molecule in isolation exhibits MBL. The results indicate limitations on the applicability of classical molecular simulations in modeling thermal transport in molecular junctions.