Thangavadivale Vargini G, Tendera Lukas, Bertermann Rüdiger, Radius Udo, Beweries Torsten, Perutz Robin N
Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
Institut für Anorganische Chemie, Julius-Maximilians-Universität, Am Hubland, 97074 Würzburg, Germany.
Faraday Discuss. 2023 Aug 11;244(0):62-76. doi: 10.1039/d2fd00171c.
Nickel fluoride complexes of the type [Ni(F)(L)(Ar)] (L = phosphine, Ar = fluorinated arene) are well-known to form strong halogen and hydrogen bonds in solution and in the solid state. A comprehensive study of such non-covalent interactions using bis(carbene) complexes as acceptors and suitable halogen and hydrogen bond donors is presented. In solution, the complex [Ni(F)(iPrIm)(CF)] forms halogen and hydrogen bonds with iodopentafluorobenzene and indole, respectively, which have formation constants () an order of magnitude greater than those of structurally related phosphine supported nickel fluorides. Co-crystallisation of this complex and its backbone-methylated analogue [Ni(F)(iPrMeIm)(CF)] with 1,4-diiodotetrafluorobenzene produces halogen bonding adducts which were characterised by X-ray analysis and F MAS solid state NMR analysis. Differences in the chemical shifts between the nickel fluoride and its halogen bonding adduct are well in line with data that were obtained from titration studies in solution.
[Ni(F)(L)(Ar)]型（L = 膦，Ar = 氟化芳烃）的氟化镍配合物在溶液和固态中形成强卤素键和氢键是众所周知的。本文介绍了一项以双（卡宾）配合物作为受体以及合适的卤素键和氢键供体对这类非共价相互作用进行的全面研究。在溶液中，配合物[Ni(F)(iPrIm)(CF)]分别与五氟碘苯和吲哚形成卤素键和氢键，其形成常数（）比结构相关的膦负载氟化镍的形成常数大一个数量级。该配合物及其骨架甲基化类似物[Ni(F)(iPrMeIm)(CF)]与1,4 - 二碘四氟苯共结晶产生卤素键加合物，通过X射线分析和F MAS固态核磁共振分析对其进行了表征。氟化镍与其卤素键加合物之间化学位移的差异与溶液滴定研究获得的数据完全一致。
