Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II)
Author(s)
Payne, Michael T; Neumann, Constanze N; Stavitski, Eli; Dincǎ, Mircea
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We report synthetic strategies for installing platinum group metals (PGMs: Pd, Rh, Ir, and Pt) on a scorpionate-derived linker (TpmC*) within a metal-organic framework (MOF), both by room-temperature postsynthetic metalation and by direct solvothermal synthesis, with a wide range of metal loadings relevant for fundamental studies and catalysis. In-depth studies for the palladium adduct Pd(II)@Zr-TpmC* by density-functional-theory-assisted extended X-ray absorption fine structure spectroscopy reveals that the rigid MOF lattice enforces a close Pd(II)-Napical interaction between the bidentate palladium complex and the third uncoordinated pyrazole arm of the TpmC* ligand (Pd-Napical = 2.501 ± 0.067 Å), an interaction that is wholly avoided in molecular palladium scorpionates.
Date issued
2021Department
Massachusetts Institute of Technology. Department of ChemistryJournal
Inorganic Chemistry
Publisher
American Chemical Society (ACS)
Citation
Payne, Michael T, Neumann, Constanze N, Stavitski, Eli and Dincǎ, Mircea. 2021. "Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II)." Inorganic Chemistry, 60 (16).
Version: Author's final manuscript