In this paper, we investigate two extensions of the concept of vibrationally mediated chemistry, from small molecules in the gas phase to small molecules in matrices and at surfaces. Exemplarily, we consider the systems HCl/DCl in Ar, and NH₃/ND₃ at Cu (111). The transition from isolated systems to the condensed phase calls for new quantum dynamical techniques, and it allows to predict new phenomena. For the case of matrix isolation, we propagate three-dimensional wavepackets representing photodissociated H- or D-atoms which penetrate from the initial cage into the lattice provided by the matrix. The cage exit probabilities are found to depend not only on the initial vibrational, but also on the rotational states, due to the environmental (O_h) symmetry provided by the (fcc) lattice of the matrix. As a consequence, we suggest the extension from vibrationally to rotationally, or rovibrationally mediated chemistry for matrix isolated molecules. For the case of molecules at surfaces, we adopt Gadzuk's jumping wavepacket plus incoherent averaging scheme, applied to an extended two-dimensional Antoniewicz-type model for the surface-molecule bond plus the vibrational coordinate which lends itself to preferential vibrational excitation, (here the umbrella mode of ammonia). The desorption depends selectively on the initial vibrational state. As a consequence, we suggest the extension of traditional desorption induced by electronic transitions (DIET) to a vibrationally mediated IR+UV DIET scheme which may be used e.g. for enrichment of specific isotopomers at surfaces.