Open AccessComplexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II)
Author(s) -
Michael T. Payne,
Constanze N. Neumann,
Eli Stavitski,
Mircea Dincă
Publication year - 2021
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.1c00941
Subject(s) - chemistry , palladium , metalation , metal , platinum , denticity , metal organic framework , catalysis , density functional theory , adduct , linker , platinum group , ligand (biochemistry) , inorganic chemistry , stereochemistry , adsorption , computational chemistry , organic chemistry , biochemistry , receptor , computer science , operating system
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.
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