Solution Spectroscopic Analysis of Ligand Exchange in Uranium Mono-Oxo Complexes

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-06 DOI:10.1021/acs.inorgchem.6c03607

Florian Ressnik, Tyler-Rayne Nero, Maximilian G. Bernbeck, Johannes Leisen, Bess Vlaisavljevich, Julie E. Niklas, Henry S. La Pierre

引用次数: 0

Abstract

Four uranium mono-oxo imidophosphorane complexes with a closed set of systematically changed substituents (pyrrolidine vs piperidine and introduction of one tert-butyl group) are presented. All complexes exhibit an inverse trans-influence (ITI). The rapid exchange of axial and equatorial ligands at room temperature, the unique ³¹P nuclear magnetic resonance (NMR) handle of the ligands, and the complexes’ overall closed-shell singlet ground state facilitate the determination of ligand-exchange barriers via variable-temperature (VT) and exchange spectroscopy (EXSY) NMR. Computational analysis delineates electronic and steric contributions to the experimentally determined exchange barriers.

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铀单氧配合物配体交换的溶液光谱分析

摘要：介绍了四种铀单氧亚胺磷烷配合物，它们具有一组封闭的系统改变取代基（吡咯烷对哌啶和引入一个叔丁基）。所有配合物均表现出逆反影响（ITI）。轴向配体和赤道配体在室温下的快速交换，配体独特的31P核磁共振（NMR）手柄，以及配合物整体的闭壳单重态基态，便于通过变温（VT）和交换光谱（EXSY） NMR确定配体交换势垒。计算分析描述了电子和空间对实验确定的交换势垒的贡献。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.