Activation of X–H Bonds (X = N, P, O, S) with SCS Pincer Palladium Complexes: A Theoretical Study



Activation of X–H bonds with SCS pincer palladium complexes featuring methanediide and indenediide backbones was studied by DFT calculations. Me2NH, Me2PH, MeOH, MeSH, PhOH, and PhSH were chosen as model substrates. Different products were considered for these addition reactions: simple adduct (X coordination), 1,2-addition across the Pd–C and Pd–S bonds, 1,3-addition (if possible), as well as oxidative addition at Pd. For the methanediide system, 1,2-PdC adducts were predicted to be the most favored activation products. For the indenediide system, 1,3-PdC and 1,2-PdC additions are conceivable. This theoretical study suggests that methanediide and indenediide Pd complexes may be interesting candidates for catalytic transformations involving X–H bond activation, typically hydrofunctionalization reactions.