Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II)

We report synthetic strategies for installing platinum group metals (PGMs: Pd, Rh, Ir, and Pt) on a scorpionate-derived linker (TpmC*) within metal-organic framework (MOF), both by room-temperature postsynthetic metalation direct solvothermal synthesis, with wide range of metal loadings relevant fundamental studies catalysis. In-depth the palladium adduct Pd(II)@Zr-TpmC* density-functional-theory-assisted extended X-ray absorption fine structure spectroscopy reveals that rigid MOF lattice enforces close Pd(II)-Napical interaction between bidentate complex third uncoordinated pyrazole arm TpmC* ligand (Pd-Napical = 2.501 ± 0.067 A), an is wholly avoided in molecular scorpionates.