Reichl Stephan, Riesinger Christoph, Scheer Manfred
Institute of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany.
Angew Chem Int Ed Engl. 2023 Sep 4;62(36):e202307696. doi: 10.1002/anie.202307696. Epub 2023 Jul 28.
By the reaction of [CpFe(η -As )] (I) (Cp=C Me ) with main group nucleophiles, unique functionalized products with η -coordinated polyarsenide (As ) units (n=5, 6, 20) are obtained. With carbon-based nucleophiles such as MeLi or KBn (Bn=CH Ph), the anionic organo-substituted polyarsenide complexes, [Li(2.2.2-cryptand)][CpFe(η -As Me)] (1 a) and [K(2.2.2-cryptand)][CpFe{η -As (CH Ph)}] (1 b), are accessible. The use of KAsPh leads to a selective and controlled extension of the As unit and the formation of the monoanionic compound [K(2.2.2-cryptand][CpFe(η -As Ph )] (2). When I is reacted with [M]As(SiMe ) (M=Li ⋅ THF; K), the formation of the largest known anionic polyarsenide unit in [M'(2.2.2-cryptand)] [(CpFe) {μ -η :η :η :η :η :η -As }] (3) occurred (M'=Li (3 a), K (3 b)).
通过[CpFe(η⁵ -As₅)]（I）（Cp = C₅Me₅）与主族亲核试剂的反应，可得到具有η⁵配位多砷化物（Asₙ）单元（n = 5、6、20）的独特功能化产物。使用碳基亲核试剂如MeLi或KBn（Bn = CH₂Ph），可得到阴离子有机取代多砷化物配合物[Li(2.2.2 - 穴醚)][CpFe(η⁵ -As₅Me)]（1 a）和[K(2.2.2 - 穴醚)][CpFe{η⁵ -As₅(CH₂Ph)}]（1 b）。使用KAsPh可导致As单元的选择性和可控扩展，并形成单阴离子化合物[K(2.2.2 - 穴醚][CpFe(η⁵ -As₁₀Ph₅)]（2）。当I与[M]As(SiMe₃)（M = Li·THF；K）反应时，会形成[M'(2.2.2 - 穴醚)] [(CpFe)₂{μ -η⁵:η⁵:η⁵:η⁵:η⁵:η⁵ -As₁₂}]（3）中已知的最大阴离子多砷化物单元（M' = Li（3 a），K（3 b））。
