结晶膦基官能化的中离子烯烃（p-MIOs）。
Crystalline phosphino-functionalized mesoionic olefins (p-MIOs).
作者信息
Merschel Arne, Vishnevskiy Yury V, Neumann Beate, Stammler Hans-Georg, Ghadwal Rajendra S
机构信息
Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, D-33615, Bielefeld, Germany.
出版信息
Dalton Trans. 2022 May 31;51(21):8217-8222. doi: 10.1039/d2dt01314b.
Phosphino-functionalized mesoionic olefins (p-MIOs), (iMIC)CHR (iMIC = PhC{N(Dipp)}C(PPh)C, Dipp = 2,6-iPrCH; R = H 4a or Ph 4b), derived from a 1,3-imidazole-based mesoionic carbene (iMIC) are reported. The p-MIOs 4a (blue) and 4b (green) are crystalline solids and have been characterized by NMR spectroscopy and X-ray diffraction as well as DFT calculations. The calculated proton affinities of 4a (291.3 kcal mol) and 4b (288.1 kcal mol) support their remarkable basicity that exceeds that of classical NHCs. Treatment of 4a with (MeS)AuCl (and AgOTf) affords the dinuclear gold compounds (4a)Au (5-X) (X = Cl or OTf) with a short Au⋯Au distance of 3.130(2) Å for 5-Cl. The reaction of 4a with the main-group reagent PhBCl yields the boronium cation [(4a)BPhCl]Cl (6).
据报道，从基于1,3 - 咪唑的中氮茚卡宾（iMIC）衍生出膦功能化的中氮茚烯烃（p - MIOs），即(iMIC)CHR（iMIC = PhC{N(Dipp)}C(PPh)C，Dipp = 2,6 - iPr₂CH；R = H 4a或Ph 4b）。p - MIOs 4a（蓝色）和4b（绿色）为结晶固体，已通过核磁共振光谱、X射线衍射以及密度泛函理论计算进行了表征。计算得出的4a（291.3 kcal mol⁻¹）和4b（288.1 kcal mol⁻¹）的质子亲和能证明了它们具有超过传统氮杂环卡宾的显著碱性。用(MeS)AuCl（和AgOTf）处理4a得到双核金化合物(4a)Au（5 - X）（X = Cl或OTf），对于5 - Cl，Au⋯Au距离短至3.130(2) Å。4a与主族试剂PhBCl反应生成硼鎓阳离子[(4a)BPhCl]Cl（6）。
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