(Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals

ChemistryEurope Pub Date : 2024-10-30 DOI:10.1002/ceur.202400061

Dr. Moritz Scharnhölz, Dr. Jose Juan Gamboa Carballo, Dr. Nils Trapp, Dr. Rene Verel, Dr. Peter Coburger, Prof. Dr. Hansjörg Grützmacher

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Abstract

Dehalogenation of (PBr)₂C₂(PPh₃)₂ with potassium graphite, KC₈, leads to C_s-P₄C₄(PPh₃)₄, which can be viewed as a PPh₃ adduct of a C_s-symmetric P₄C₄ cage. An isolable intermediate was found and in combination with DFT calculations, the structure of a S₄-symmetric P₄C₄(PPh₃)₄ cage is proposed for this species. That a 1,3-diphosphete type Ph₃P→P₂C₂←PPh₃ heterocycle is a short-lived intermediate in the dehalogenation reaction is indicated by trapping experiments which allowed to isolate and fully characterize the [Fe(CO)₄] complexes [Fe(CO)₄(κ-P−P₂C₂{PPh₃}₂] and [(Fe(CO)₄)₂(μ₂-κ-P−P₂C₂{PPh₃}₂]. The conversion of S₄-P₄C₄(PPh₃)₄ to C_s-P₄C₄(PPh₃)₄ prompted a (re)investigation of the isomerization of various P₄X₄ species (X=S, NH, NMe; CH₂), which shows that these proceed on Minimum Energy Reaction Pathways (MERPs) with two transition states embracing one intermediate. In contrast, the isomerization S₄-P₄C₄(PR₃)₄ to C_s-P₄C₄(PR₃)₄ is a one-step process.

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（Ph3P）4C4P4：取代对磷化碳自由基寡聚化的影响

（PBr）2C2(PPh3)2与石墨钾KC8脱卤化反应生成Cs-P4C4(PPh3)4，可看作是cs对称P4C4笼的PPh3加合物。发现了一个可分离的中间产物，并结合DFT计算，提出了该物种的s4对称P4C4(PPh3)4笼结构。捕集实验表明，1,3-二磷酸盐型Ph3P→P2C2←PPh3杂环是脱卤反应的短寿命中间体，分离并完整表征了[Fe(CO)4]配合物[Fe(CO)4(κ-P−P2C2{PPh3}2]和[(Fe(CO)4)2(μ2-κ-P−P2C2{PPh3}2]。S4-P4C4(PPh3)4转化为Cs-P4C4(PPh3)4促使人们（重新）研究各种P4X4的异构化(X=S， NH, NMe；这表明这些反应是在最小能量反应途径（merp）上进行的，其中两个过渡态包含一个中间体。相反，S4-P4C4(PR3)4到Cs-P4C4(PR3)4的异构化是一个一步过程。

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