Probing Homogeneous Catalysts and Precatalysts in Solution by Exchange-Mediated Overhauser Dynamic Nuclear Polarization NMR
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2024-05-08
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Journal Article
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Abstract
Triphenylphosphine (PPh₃) is a ubiquitous ligand in organometallic chemistry that has been shown to give enhanced ³¹P NMR signals at high magnetic field via a scalar-dominated Overhauser effect dynamic nuclear polarization (OE DNP). However, PPh₃ can only be polarized via DNP in the free form, while the coordinated form is DNP-inactive. Here, we demonstrate the possibility of enhancing the ³¹P NMR signals of coordinated PPh3 in metal complexes in solution at room temperature by combining Overhauser effect DNP and chemical exchange between the free and coordinated PPh₃ forms. With this method, we successfully obtain ³¹P DNP enhancements of up to 2 orders of magnitude for the PPh₃ ligands in Rh(I), Ru(II), Pd(II), and Pt(II) complexes, and we show that the DNP enhancements can be used to determine the activation energy of the ligand exchange reaction.
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published
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146 (18)
Pages / Article No.
12587 - 12594
Publisher
American Chemical Society
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Subject
Electromagnetic radiation; Ligands; Metals; Nuclear magnetic resonance spectroscopy; Polarization
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03872 - Copéret, Christophe / Copéret, Christophe