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How Solid Surfaces Control Stability and Interactions of Supported Cationic Cu I (dppf) Complexes─A Solid-State NMR Study.
- Source :
-
Inorganic chemistry [Inorg Chem] 2023 May 15; Vol. 62 (19), pp. 7283-7295. Date of Electronic Publication: 2023 May 03. - Publication Year :
- 2023
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Abstract
- Organometallic complexes are frequently deposited on solid surfaces, but little is known about how the resulting complex-solid interactions alter their properties. Here, a series of complexes of the type Cu(dppf)(L <subscript> x </subscript> ) <superscript>+</superscript> (dppf = 1,1'-bis(diphenylphosphino)ferrocene, L <subscript> x </subscript> = mono- and bidentate ligands) were synthesized, physisorbed, ion-exchanged, or covalently immobilized on solid surfaces and investigated by <superscript>31</superscript> P MAS NMR spectroscopy. Complexes adsorbed on silica interacted weakly and were stable, while adsorption on acidic γ-Al <subscript>2</subscript> O <subscript>3</subscript> resulted in slow complex decomposition. Ion exchange into mesoporous Na-[Al]SBA-15 resulted in magnetic inequivalence of <superscript>31</superscript> P nuclei verified by <superscript>31</superscript> P- <superscript>31</superscript> P RFDR and <superscript>1</superscript> H- <superscript>31</superscript> P FSLG HETCOR. DFT calculations verified that a MeCN ligand dissociates upon ion exchange. Covalent immobilization via organic linkers as well as ion exchange with bidentate ligands both lead to rigidly bound complexes that cause broad <superscript>31</superscript> P CSA tensors. We thus demonstrate how the interactions between complexes and functional surfaces determine and alter the stability of complexes. The applied Cu(dppf)(L <subscript> x </subscript> ) <superscript>+</superscript> complex family members are identified as suitable solid-state NMR probes for investigating the influence of support surfaces on deposited inorganic complexes.
Details
- Language :
- English
- ISSN :
- 1520-510X
- Volume :
- 62
- Issue :
- 19
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 37133820
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.3c00351