The photophysical properties of transition metal complexes have for many years been the subject of intense interest and have been exploited for myriad applications, from synthetic and preparative chemistry to artificial photosynthesis. A variety of electronic transitions are possible when a transition metal complex absorbs light. For metal complexes with 1 to 9 d electrons, d-d transitions can occur. Another important class of electronic transition is metal-to-ligand charge transfer (MLCT), which involves transitions from a d-orbital to low-lying antibonding orbitals on the ligands (e.g., π*) and generally feature intense absorption bands. The resulting charge separation can engender reactivity not accessible in the ground state. For example, [Ru(2,2ʹ-bipyridine)] 2+ is both a better oxidant and better reductant in the excited state, and this characteristic is an important feature of the photocatalysts used in photoredox processes. Depending on the nature of the orbitals involved in the electronic transition (i.e. bonding, antibonding or nonbonding), excitation may strengthen or weaken bonds in the complex and lead to chemical reactivity. A classic example of this phenomenon is photoinduced CO dissociation from metal carbonyl complexes (e.g., M(CO)6, M = Cr, Mo, W). In this case, absorption of a photon promotes a transition from an orbital that is π-bonding to an orbital that is σ-antibonding with respect to the dative bond. Excited state reactivity in metal complexes has emerged as a broadly useful concept in synthetic chemistry. As a corollary, the discovery of previously unknown excited state reactivity, particularly with complexes with established utility in catalysis, holds the potential to enable novel and interesting transformations. In this regard, palladium is one of the most used transition metals in catalysis yet the large majority of processes developed using Pd catalysts operate under ground state conditions. Transformations that take advantage of photoexcited states during Pd catalysis remain relatively underexplored.