This work features the previously undescribed interactions of Martin’s spirosilane with different types of N-heterocyclic carbenes (NHCs). The level of interaction proved to be strongly dependent on the size of the Lewis base and could vary from the formation of isolable classical Lewis adducts to abnormal Lewis adducts, as evidenced by X-ray diffraction structure analyses and NMR studies. It has been found that abnormal adducts could be used as precursors for the synthesis of anionic NHCs bearing a weakly coordinating siliconate component. Complexation of these new types of carbenes with gold(I) and copper(I) has been efficiently accomplished. DFT calculations performed on the siliconate-based anionic NHC ligands revealed a high-lying HOMO and therefore a strong σ-donor character.

中文翻译：

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稳定的五配位硅（IV）-NHC加合物的合成：阴离子N-杂环碳烯配体的入口

这项工作的特点是以前未描述的马丁螺硅烷与不同类型的N-杂环卡宾（NHC）的相互作用。X射线衍射结构分析和NMR研究证明，相互作用的水平在很大程度上取决于Lewis碱的大小，并且可能从可分离的经典Lewis加合物的形成到异常Lewis加合物的变化而变化。已经发现，异常加合物可以用作具有弱配位硅酸酯组分的阴离子NHCs的合成的前体。这些新型卡宾与金（I）和铜（I）的络合已得到有效完成。在基于硅酸盐的阴离子NHC配体上进行的DFT计算显示出高度的HOMO，因此具有很强的σ供体特性。