(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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