Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II)
Name
1817354.pdf
Description
Accepted version
Size
1.65 MB
Format
Adobe PDF
Checksum (MD5)
11f162ebcd2d7ed0442f1d0e3e8443be
Author(s)
Payne, Michael T
Neumann, Constanze N
Stavitski, Eli
Dincǎ, Mircea
Date Issued
2021
Journal
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
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)-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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Creative Commons Attribution-Noncommercial-Share Alike
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/ACS.INORGCHEM.1C00941
