Riethmann Melanie, Föhrenbacher Steffen A, Keiling Hannes, Ignat'ev Nikolai V, Finze Maik, Radius Udo
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg 97074, Germany.
Institute for Sustainable Chemistry & Catalysis with Boron (ICB), Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg 97074, Germany.
Inorg Chem. 2024 May 6;63(18):8351-8365. doi: 10.1021/acs.inorgchem.4c00750. Epub 2024 Apr 19.
We herein report the convenient synthesis of different -heterocyclic carbene (NHC)- and cyclic (alkyl)(amino)carbene (cAAC)-ligated copper cations using the weakly coordinating tris(pentafluoroethyl)trifluorophosphate counterion ( anion, [(CF)PF]). The reaction of the fluorido complexes [(carbene)CuF] (carbene = NHC, cAAC) - and the tris(pentafluoroethyl)difluorophosphorane (CF)PF in the presence of alkynes or arenes led to fluoride transfer from Cu to the phosphorane with formation of the cationic transition metal complexes [(carbene)Cu()] and the weakly coordinating counteranion [(CF)PF] (). Using this method, the complexes [(IDipp)Cu()] (IDipp = 1,3-bis(2,6-di--propylphenyl)-imidazolin-2-ylidene; = PhC≡CPh, ; PhC≡CMe, ), [(cAAC)Cu()] (cAAC = 1-(2,6-di--propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene; PhC≡CPh, ; PhC≡CMe, ), [(SIDipp)Cu(CMe)] (), (SIDipp = 1,3-bis(2,6-di--propylphenyl)-imidazolidine-2-ylidene), and [(cAAC)Cu(CMe)] () have been synthesized and characterized. The complexes [(IDipp)Cu(CMe)] () and [(cAAC)Cu(CMe)] () have been used as catalysts for the copper(I)-catalyzed cycloaddition of benzyl azide to terminal alkynes.
我们在此报告了使用弱配位的三（五氟乙基）三氟磷酸根抗衡离子（阴离子，[(CF₃)₂PF₃]）方便地合成不同的杂环卡宾（NHC）和环（烷基）（氨基）卡宾（cAAC）配位的铜阳离子。在炔烃或芳烃存在下，氟配合物[(卡宾)CuF]（卡宾 = NHC，cAAC）与三（五氟乙基）二氟磷烷（(CF₃)₂PF）反应，导致氟从铜转移到磷烷上，形成阳离子过渡金属配合物[(卡宾)Cu(⁺)]和弱配位的抗衡阴离子[(CF₃)₂PF₃⁻]。使用这种方法，合成并表征了配合物[(IDipp)Cu(⁺)]（IDipp = 1,3 - 双（2,6 - 二 - 异丙基苯基） - 咪唑啉 - 2 - 亚基；⁻ = PhC≡CPh，⁻；PhC≡CMe，⁻），[(cAAC)Cu(⁺)]（cAAC = 1 - （2,6 - 二 - 异丙基苯基） - 3,3,5,5 - 四甲基 - 吡咯烷 - 2 - 亚基；⁻ PhC≡CPh，⁻；PhC≡CMe，⁻），[(SIDipp)Cu(C≡CMe)]（⁻），（SIDipp = 1,3 - 双（2,6 - 二 - 异丙基苯基） - 咪唑烷 - 2 - 亚基），和[(cAAC)Cu(C≡CMe)]（⁻）。配合物[(IDipp)Cu(C≡CMe)]（⁻）和[(cAAC)Cu(C≡CMe)]（⁻）已被用作铜（I）催化苄基叠氮化物与末端炔烃环加成反应的催化剂。
