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 a metal-organic framework (MOF), both by room-temperature postsynthetic metalation and by direct solvothermal synthesis, with a wide range of metal loadings r...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2022
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| Online Access: | https://hdl.handle.net/1721.1/143952 |
| _version_ | 1826215542304800768 |
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| author | Payne, Michael T Neumann, Constanze N Stavitski, Eli Dincǎ, Mircea |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Payne, Michael T Neumann, Constanze N Stavitski, Eli Dincǎ, Mircea |
| author_sort | Payne, Michael T |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T16:34:19Z |
| format | Article |
| id | mit-1721.1/143952 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T16:34:19Z |
| publishDate | 2022 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1439522023-01-10T15:10:32Z 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 Massachusetts Institute of Technology. Department of Chemistry 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. 2022-07-22T11:57:49Z 2022-07-22T11:57:49Z 2021 2022-07-22T11:54:23Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/143952 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). en 10.1021/ACS.INORGCHEM.1C00941 Inorganic Chemistry Creative Commons Attribution-Noncommercial-Share Alike https://creativecommons.org/licenses/by/4.0/ application/pdf American Chemical Society (ACS) DOE repository |
| spellingShingle | Payne, Michael T Neumann, Constanze N Stavitski, Eli Dincǎ, Mircea Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II) |
| title | Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II) |
| title_full | Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II) |
| title_fullStr | Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II) |
| title_full_unstemmed | Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II) |
| title_short | Complexes of Platinum Group Metals with a Conformationally Locked Scorpionate in a Metal–Organic Framework: An Unusually Close Apical Interaction of Palladium(II) |
| title_sort | complexes of platinum group metals with a conformationally locked scorpionate in a metal organic framework an unusually close apical interaction of palladium ii |
| url | https://hdl.handle.net/1721.1/143952 |
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