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通过交换介导的奥弗豪泽动态核极化核磁共振探测溶液中的均相催化剂和前催化剂。

Probing Homogeneous Catalysts and Precatalysts in Solution by Exchange-Mediated Overhauser Dynamic Nuclear Polarization NMR.

作者信息

Rao Yu, De Biasi Federico, Wei Ran, Copéret Christophe, Emsley Lyndon

机构信息

Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.

Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093 Zürich, Switzerland.

出版信息

J Am Chem Soc. 2024 May 8;146(18):12587-12594. doi: 10.1021/jacs.4c01570. Epub 2024 Apr 29.

DOI:10.1021/jacs.4c01570
PMID:38685488
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11082894/
Abstract

Triphenylphosphine (PPh) is a ubiquitous ligand in organometallic chemistry that has been shown to give enhanced P NMR signals at high magnetic field via a scalar-dominated Overhauser effect dynamic nuclear polarization (OE DNP). However, PPh 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 P NMR signals of coordinated PPh in metal complexes in solution at room temperature by combining Overhauser effect DNP and chemical exchange between the free and coordinated PPh forms. With this method, we successfully obtain P DNP enhancements of up to 2 orders of magnitude for the PPh 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.

摘要

三苯基膦（PPh）是有机金属化学中一种普遍存在的配体，已证明通过标量主导的奥弗豪泽效应动态核极化（OE DNP）在高磁场下能增强磷核磁共振信号。然而，PPh只有以游离形式才能通过DNP进行极化，而配位形式则无DNP活性。在此，我们证明了通过结合奥弗豪泽效应DNP和游离与配位PPh形式之间的化学交换，在室温下增强溶液中金属配合物中配位PPh的磷核磁共振信号的可能性。通过这种方法，我们成功地使Rh（I）、Ru（II）、Pd（II）和Pt（II）配合物中PPh配体的磷DNP增强高达2个数量级，并且我们表明DNP增强可用于确定配体交换反应的活化能。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/10ed59c7da48/ja4c01570_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/7f6b3e4a997a/ja4c01570_0007.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/8e1c1c93ef1c/ja4c01570_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/10ed59c7da48/ja4c01570_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/7f6b3e4a997a/ja4c01570_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/86e83415dba8/ja4c01570_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/b2edb998bf25/ja4c01570_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/c19b1bbc3edb/ja4c01570_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/8575a9d7e39d/ja4c01570_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/2ab530988290/ja4c01570_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/8e1c1c93ef1c/ja4c01570_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3035/11082894/10ed59c7da48/ja4c01570_0006.jpg

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