Esingle bondH bond cleavage by [{PC(sp²)P}Pd(PMe₃)] (1, PC(sp²)P = ⁱPr₂Psingle bondC₆H₄single bondCsingle bondC₆H₄single bondPⁱPr₂) of alcohols led to a series of new square-planar tridentate palladium alkoxides, [{PC(sp³)HP}Pd(OⁱPr)] (3), [{PC(sp³)HP}Pd(O^tBu)] (4), and [{PC(sp³)HP}Pd(OPh)] (5, PC(sp³)HP = bis[2-(di-iso-propylphosphino)phenyl]methyl). The analogous reaction with amines led to the formation of [{PC(sp³)HP}Pd(NPh₂)] (6) and [{PC(sp³)HP}Pd(NHMes)] (7). The molecular structure of 7 was further probed by a CO₂ insertion reaction into the Pdsingle bondN bond, yielding the corresponding carbamate 8. The molecular structures of 3–8 were determined by single-crystal X-ray diffraction and conform to the corresponding solution structures as determined by NMR spectroscopy. The reactivity of carbene 1 towards alcohols and amines is dictated by the nucleophilic/basic character at the carbene backbone carbon atom, the pK_a and bond dissociation energy of the Esingle bondH bond (E = N, O), and the steric properties of the organic substrates used.