Please do not adjust margins Please do not adjust margins the CH3 group by 0.32 e and 0.25 e, respectively (see ESI, Table for tabular data). We interpret these data as indicative of an uncommon Pd-to-CH3 MLCT process. This contrasts what has been proposed for the electronic transition underpinning the photochemistry of (α-diimine)Pd complexes, such as 3, via traditional d-to-π* MLCT that populates an ancillary ligandcentred orbital. The potential to stimulate charge transfer to unactivated alkyl groups (i.e. lacking groups that stabilize radicals) of an organometallic complex highlights that π-based ancillary ligands are not essential for achieving mild, efficient photochemistry in Pd complexes. It may also be inferred that there may exist a reservoir of untapped photochemical reactivity in organo-Pd(II) complexes previously presumed to be photochemically inert due to a lack of ancillary ligand-based chromophores. For comparative purposes the truncated complex [PhN=C(Me)C(Me)=NPh]Pd(CH3)Cl (S3) was also examined. The optimal functional, based again on best agreement of experimental and calculated absorption spectra (see ESI, Figure ), was M06 in this case. Difference density isosurface calculations for S3 confirmed an expected d-to-π* MLCT transition at 459 nm along with another transition at 458 nm which appears to have Cl-to-π* character (Figure ). Population analysis of this (α-diimine)Pd(II) system showed an average loss of 0.29 e at Pd and gain of 0.5 e on the diimine ligand (see ESI, Table for tabular data). A significant change in Pd(II)-C bond order was not observed for this complex, which is not yet understood; one rationalization could be the need for thermalization of the Franck-Condon state to another excited state (e.g., S1) prior to weakening of the Pd(II)-C bond.