含有1,2 - 二磷杂 - 1,3 - 丁二烯及其自由基阴离子的五元杂环化合物的合成与结构
Syntheses and Structures of 5-Membered Heterocycles Featuring 1,2-Diphospha-1,3-Butadiene and Its Radical Anion.
作者信息
Sharma Mahendra K, Weinert Hanns M, Li Bin, Wölper Christoph, Henthorn Justin T, Cutsail George E, Haberhauer Gebhard, Schulz Stephan
机构信息
Institute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstraße 5-7, 45141, Essen, Germany.
Max Planck Institute for Chemical Energy Conversion (MPI-CEC), Stiftstrasse 34-36, 45470, Mülheim an der Ruhr, Germany.
出版信息
Angew Chem Int Ed Engl. 2023 Oct 2;62(40):e202309466. doi: 10.1002/anie.202309466. Epub 2023 Aug 29.
LGa(P OC)cAAC 2 features a 1,2-diphospha-1,3-butadiene unit with a delocalized π-type HOMO and a π*-type LUMO according to DFT calculations. [LGa(P OC)cAAC][K(DB-18-c-6)] 3[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene radical anion 3⋅ was isolated from the reaction of 2 with KC and dibenzo-18-crown-6. 3 reacted with [Fc][B(C F ) ] (Fc=ferrocenium) to 2 and with TEMPO to [L Ga(P OC)cAAC][K(DB-18-c-6)] 4[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene anion 4 . The solid state structures of 2, 3K(DB-18-c-6], and 4[K(DB-18-c-6] were determined by single crystal X-ray diffraction (sc-XRD).
根据密度泛函理论计算，LGa(P OC)cAAC 2具有一个1,2 - 二磷杂-1,3 - 丁二烯单元，其具有离域的π型最高占据分子轨道（HOMO）和π*型最低未占据分子轨道（LUMO）。从2与KC和二苯并-18 - 冠-6的反应中分离出含有1,2 - 二磷杂-1,3 - 丁二烯自由基阴离子3⋅的[LGa(P OC)cAAC][K(DB - 18 - c - 6)] 3[K(DB - 18 - c - 6]。3与[Fc][B(C F ) ]（Fc = 二茂铁鎓）反应生成2，与2,2,6,6 - 四甲基哌啶-1 - 氧基（TEMPO）反应生成含有1,2 - 二磷杂-1,3 - 丁二烯阴离子4的[L Ga(P OC)cAAC][K(DB - 18 - c - 6)] 4[K(DB - 18 - c - 6]。通过单晶X射线衍射（sc - XRD）确定了2、3K(DB - 18 - c - 6]和4[K(DB - 18 - c - 6]的固态结构。
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