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

Payne, Michael T.; Neumann, Constanze N.; Stavitski, Eli; Dincǎ, Mircea

doi:10.1021/acs.inorgchem.1c00941

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

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Citation

Payne, M. T., Neumann, C. N., Stavitski, E., & Dincǎ, M. (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), 11764-11774. doi:10.1021/acs.inorgchem.1c00941.

Cite as: https://hdl.handle.net/21.11116/0000-0009-08A1-8

Abstract

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)–N_apical interaction between the bidentate palladium complex and the third uncoordinated pyrazole arm of the TpmC* ligand (Pd–N_apical = 2.501 ± 0.067 Å), an interaction that is wholly avoided in molecular palladium scorpionates.