Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstrasse 34/36, D-14195 Berlin, Germany.
Inorg Chem. 2021 Nov 1;60(21):16734-16753. doi: 10.1021/acs.inorgchem.1c02599. Epub 2021 Oct 17.
A scalable synthesis of the novel and highly reactive [Tc(OH)(CO)(PPh)] cation is described. The ligand-exchange chemistry of this compound with neutral ligands coordinating through C, N, O, S, Se, and Te has been explored systematically. The complexes either retain the original tricarbonyl core under exclusive exchange of the aqua ligand or form dicarbonyl complexes by thermal decarbonylation. Ligand exchange reactions starting from [Tc(OH)(CO)(PPh)] proceed under mild conditions and are generally almost quantitative. Some of the formed complexes are remarkably stable and inert, while others provide products with one labile ligand for further reactions. The derived complexes of the type [Tc(L)(CO)(PPh)] and [Tc(L)(CO)(PPh)] represent an interesting opportunity for the development of Tc complexes with potential use in radiopharmacy. The ready displacement of the aqua ligand highlights the synthetic value of [Tc(OH)(CO)(PPh)] as a reactive entry point for further studies in the little explored field of the organometallic chemistry of technetium.
描述了一种新型且高反应性的[Tc(OH)(CO)(PPh)]阳离子的可扩展合成方法。系统探索了该化合物与通过 C、N、O、S、Se 和 Te 配位的中性配体的配位交换化学。这些配合物在仅交换水合配体的情况下保留原始的三羰基核心，或者通过热脱羰形成二羰基配合物。从[Tc(OH)(CO)(PPh)]开始的配体交换反应在温和条件下进行，通常几乎是定量的。一些形成的配合物非常稳定和惰性，而另一些则提供具有一个不稳定配体的产物，以进行进一步的反应。形成的[Tc(L)(CO)(PPh)]和[Tc(L)(CO)(PPh)]型配合物为开发具有潜在放射性药物用途的 Tc 配合物提供了一个有趣的机会。水合配体的易取代突出了[Tc(OH)(CO)(PPh)]作为进一步研究铼有机金属化学这一探索较少领域的反应性起点的合成价值。
