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一段愉悦之旅：六氟化钨和五氟化钨与氮杂环卡宾及环（烷基）（氨基）卡宾的相遇

A Joyful Journey: Tungsten(VI) and Tungsten(V) Fluorides Meet N-Heterocyclic Carbenes and Cyclic (Alkyl)(Amino)Carbenes.

作者信息

Riethmann Melanie, Eyßelein Leonhard, Krummenacher Ivo, Bertermann Rüdiger, Braunschweig Holger, Gerken Michael, Finze Maik, Radius Udo

机构信息

Institute of Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.

Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.

出版信息

Angew Chem Int Ed Engl. 2025 Jun 17;64(25):e202504498. doi: 10.1002/anie.202504498. Epub 2025 May 15.

DOI:10.1002/anie.202504498
PMID:40227880
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12171349/
Abstract

The first complexation of tungsten(VI) fluoride with N-heterocyclic carbenes (NHCs) and a cyclic (alkyl)(amino) carbene (cAAC) is reported, which led to formation of the complexes [(NHC)WF] (NHC = IiPr, 1; BIiPr, 2; IMes, 3; IDipp, 4; and SIDipp, 5) and [(cAAC)WF] 6. Solid-state structural analysis revealed distorted mono-capped trigonal prismatic geometries for 2 and 3, whereas 6 adopts a pentagonal bipyramidal coordination. Reduction of 1-6 with 0.5 equivalents of TMS-pyr-TMS afforded rare tungsten(V) fluoride complexes [(NHC)WF] (NHC = IiPr, 7; BIiPr, 8; IMes, 9; IDipp, 10; and SIDipp, 11). Reduction of 6 with TMS-pyr-TMS yielded the dinuclear, fluoride-bridged complex [(cAAC)WF] 12. Subsequent addition of a second equivalent cAAC to 12 gave the mononuclear, seven-coordinated bis-carbene complex [(cAACMe)WF] 13. Magnetic susceptibility measurements and EPR spectroscopy confirm a predominantly metal-centered d¹ radical in both 12 and 13. These findings expand the scope of tungsten fluoride chemistry by providing rare examples of tungsten(VI) and tungsten(V) complexes stabilized by soft carbon-donor ligands, paving the way for further exploration.

摘要

首次报道了六氟化钨与氮杂环卡宾（NHCs）和环（烷基）（氨基）卡宾（cAAC）的络合反应，反应生成了络合物[(NHC)WF]（NHC = IiPr，1；BIiPr，2；IMes，3；IDipp，4；和SIDipp，5）以及[(cAAC)WF] 6。固态结构分析表明，2和3呈现扭曲的单帽三棱柱几何构型，而6则采用五角双锥配位构型。用0.5当量的TMS-pyr-TMS还原1 - 6得到了罕见的五氟化钨络合物[(NHC)WF]（NHC = IiPr，7；BIiPr，8；IMes，9；IDipp，10；和SIDipp，11）。用TMS-pyr-TMS还原6得到了双核、氟桥连络合物[(cAAC)WF] 12。随后向12中加入第二当量的cAAC得到了单核、七配位的双卡宾络合物[(cAACMe)WF] 13。磁化率测量和电子顺磁共振光谱证实，12和13中主要是以金属为中心的d¹自由基。这些发现通过提供由软碳供体配体稳定化的六价钨和五价钨络合物的罕见例子，扩展了氟化钨化学的范围，为进一步探索铺平了道路。

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