Systematic Study of the Stereoelectronic Properties of Trifluoromethylated Triarylphosphines and the Correlation of their Behaviour as Ligands in the Rh‐Catalysed Hydroformylation,European Journal of Inorganic Chemistry

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Systematic Study of the Stereoelectronic Properties of Trifluoromethylated Triarylphosphines and the Correlation of their Behaviour as Ligands in the Rh‐Catalysed Hydroformylation
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-11-22 , DOI: 10.1002/ejic.202000887
Daniel Herrera ₁ , Daniel Peral ₁ , Mercedes Cordón ₁ , J. Carles Bayón ₁

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The stereoelectronic properties of a series of trifluoromethylated aromatic phosphines have been studied using different approaches. The σ‐donating capability has been evaluated by nuclear magnetic resonance (NMR) spectroscopy of the selenide derivatives and the protonated form of the different trifluoromethylated phosphines. The coupling constants between phosphorous and selenium (¹J_SeP) and phosphorous and hydrogen (¹J_HP) can be predicted by empirical equations and correlate the basicity of the phosphines with the number and relative position of trifluoromethyl groups. In contrast, the π‐acceptor character of the ligands has been evaluated by measuring the frequency of the CO vibration in the infrared (IR) spectra of the corresponding Vaska type iridium complexes ([IrCl(CO)(PAr₃)₂], PAr₃=triarylphosphine). Moreover, the correlation between the electronic properties and the performance of these phosphines as ligands in the rhodium‐catalysed hydroformylation of 1‐octene has been established. Phosphines with the lowest basicity, that are those with the highest number of trifluoromethyl groups, gave rise to more active catalytic systems.

中文翻译：

三氟甲基化三芳基膦的立体电子性质及其在Rh催化加氢甲酰化中作为配体的行为相关性的系统研究

已经使用不同的方法研究了一系列三氟甲基化芳族膦的立体电子性质。σ捐赠能力已通过硒化物衍生物和不同三氟甲基化膦的质子化形式的核磁共振（NMR）光谱进行了评估。磷和硒（¹ J _SeP）与磷和氢（¹ J _HP）之间的耦合常数。）可以通过经验方程式进行预测，并将膦的碱度与三氟甲基的数量和相对位置相关联。相反，已通过测量相应的Vaska型铱配合物（[IrCl（CO）（PAr ₃）₂ ]，PAr ）的红外（IR）光谱中的CO振动频率来评估配体的π受体特性。₃ =三芳基膦）。此外，在铑催化的1-辛烯加氢甲酰化反应中，这些膦作为配体的电子性质与性能之间的相关性也已建立。具有最低碱性的膦，即具有最高数量的三氟甲基的膦，产生了更具活性的催化体系。

更新日期：2021-01-22

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