King Rhys P, Levason William, Reid Gillian
School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK.
Dalton Trans. 2021 Dec 7;50(47):17751-17765. doi: 10.1039/d1dt03339e.
The neutral complexes -[GeF(PPr)] and [GeF(κ-L)] (L = CHC(CHPPh) or P(CHCHPPh)) are obtained from [GeF(MeCN)] and the ligand in CHCl. Treatment of [GeF(PMe)] with n equivalents of TMSOTf (MeSiOSCF) leads to formation of the series [GeF(PMe)(OTf)] ( = 1, 2, 3), each of which contains six-coordinate Ge(IV) with PMe ligands and X-ray structural data confirm that the OTf groups interact with Ge(IV) to varying degrees. Unexpectedly, [GeF(PMe)(OTf)] undergoes reductive defluorination in solution, forming the Ge(II) complex, [Ge(PMe)][OTf] (and [FPMe]). The bulkier PPr leads to formation of the ionic [GeF(PrP)][OTf], containing a [GeF(PrP)] cation. [GeF{-CH(PMe)}], containing the -chelating diphosphine, also reacts with n equivalents of TMSOTf to generate [GeF{-CH(PMe)}(OTf)] ( = 1, 2, 3). As for the PMe system, the trifluoride, [GeF{-CH(PMe)}(OTf)], is unstable to reductive defluorination in solution, producing the pyramidal Ge(II) complex [Ge{(-CH(PMe)}(OTf)][OTf], whose crystal structure has been determined. The [GeF{PhP(CH)PPh}(OTf)] and [GeF{PhP(CH)PPh}(OTf)], obtained similarly from the parent tetrafluoride complex, are poorly soluble, however their structures were confirmed crystallographically. The complexes in this work have been characterised variable temperature H, F{H} and P{H} NMR studies in solution, IR spectroscopy and microanalysis and through single crystal X-ray analysis of representative examples across each series. Trends in the NMR and structural parameters are also discussed.
中性配合物 -[GeF(PPr)] 和 [GeF(κ-L)]（L = CHC(CHPPh) 或 P(CHCHPPh)）由 [GeF(MeCN)] 和 CHCl 中的配体反应得到。用 n 当量的 TMSOTf（MeSiOSCF）处理 [GeF(PMe)] 会生成系列配合物 [GeF(PMe)(OTf)]（n = 1, 2, 3），其中每个配合物都含有六配位的 Ge(IV) 以及 PMe 配体，X 射线结构数据证实 OTf 基团与 Ge(IV) 有不同程度的相互作用。出乎意料的是，[GeF(PMe)(OTf)] 在溶液中会发生还原脱氟反应，生成 Ge(II) 配合物 [Ge(PMe)][OTf]（以及 [FPMe]）。体积更大的 PPr 会导致形成离子型的 [GeF(PrP)][OTf]，其中含有 [GeF(PrP)] 阳离子。含有 - 螯合二膦的 [GeF{-CH(PMe)}] 同样会与 n 当量的 TMSOTf 反应生成 [GeF{-CH(PMe)}(OTf)]（n = 1, 2, 3）。与 PMe 体系情况相同，三氟化物 [GeF{-CH(PMe)}(OTf)] 在溶液中对还原脱氟不稳定，会生成三角锥型的 Ge(II) 配合物 [Ge{(-CH(PMe)}(OTf)][OTf]，其晶体结构已被确定。同样由母体四氟化物配合物得到的 [GeF{PhP(CH)PPh}(OTf)] 和 [GeF{PhP(CH)PPh}(OTf)] 溶解性很差，不过它们的结构已通过晶体学得到证实。本工作中的配合物通过溶液中的变温 H、F{H} 和 P{H} NMR 研究、红外光谱、微量分析以及对每个系列代表性实例的单晶 X 射线分析进行了表征。同时还讨论了 NMR 和结构参数的趋势。
