Xiang Libo, Wang Junyi, Knoblauch Niclas, Matler Alexander, Ye Qing
Institute for Inorganic Chemistry, Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg, 97074, Germany.
Department of Chemistry, Southern University of Science and Technology, 1088 Xueyuan Blvd., Xili, Nanshan District, Shenzhen, 518055, China.
Angew Chem Int Ed Engl. 2025 May 26;64(22):e202501955. doi: 10.1002/anie.202501955. Epub 2025 Apr 7.
The ortho-carboranyl carbophosphinocarbene (CPC) has been synthesized through a click-type reaction between the super strained carborane-fused borirane 1,2-BN(SiMe)-1,2-CBH and Bestmann ylide PhPCCO. The [Cl(CO)₂Ir-CPC] and [ClGa-CPC] complexes were synthesized, allowing the measurement of their Tolman electronic parameter (TEP) and the sum of Cl─Ga─Cl bond angles (∑ClGaCl), respectively. These data highlight their remarkable electron-donating ability. Further insights into its electron-donating properties were gained through theoretical calculations, including analysis of frontier orbitals and proton affinity (PA). Preliminary reactivity investigations demonstrate that the new CPC readily forms adducts with boranes and can effectively stabilize borenium cations. Its strong nucleophilicity enables reactions with carbon dioxide, while its exceptional Brønsted basicity allows it to deprotonate imidazolium to generate carbene species.
通过超张力碳硼烷稠合硼杂环丁烷1,2-BN(SiMe)-1,2-CBH与贝斯德曼叶立德PhPCCO之间的点击型反应合成了邻碳硼烷基碳膦卡宾（CPC）。合成了[Cl(CO)₂Ir-CPC]和[ClGa-CPC]配合物，分别用于测量它们的托尔曼电子参数（TEP）和Cl─Ga─Cl键角之和（∑ClGaCl）。这些数据突出了它们卓越的给电子能力。通过理论计算，包括对前线轨道和质子亲和能（PA）的分析，进一步深入了解了其给电子性质。初步的反应性研究表明，新型CPC很容易与硼烷形成加合物，并能有效稳定硼正离子。其强亲核性使其能够与二氧化碳发生反应，而其特殊的布朗斯特碱性使其能够使咪唑鎓去质子化以生成卡宾物种。
