(Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals
Abstract Dehalogenation of (PBr)2C2(PPh3)2 with potassium graphite, KC8, leads to Cs‐P4C4(PPh3)4, which can be viewed as a PPh3 adduct of a Cs‐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 propose...
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2025-01-01
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| Online Access: | https://doi.org/10.1002/ceur.202400061 |
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| author | Dr. Moritz Scharnhölz Dr. Jose Juan Gamboa Carballo Dr. Nils Trapp Dr. Rene Verel Dr. Peter Coburger Prof. Dr. Hansjörg Grützmacher |
| author_facet | Dr. Moritz Scharnhölz Dr. Jose Juan Gamboa Carballo Dr. Nils Trapp Dr. Rene Verel Dr. Peter Coburger Prof. Dr. Hansjörg Grützmacher |
| author_sort | Dr. Moritz Scharnhölz |
| collection | DOAJ |
| description | Abstract Dehalogenation of (PBr)2C2(PPh3)2 with potassium graphite, KC8, leads to Cs‐P4C4(PPh3)4, which can be viewed as a PPh3 adduct of a Cs‐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 Cs‐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 Cs‐P4C4(PR3)4 is a one‐step process. |
| format | Article |
| id | doaj-art-5e0a96c75dd64d80b6485194af15a846 |
| institution | Kabale University |
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| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley-VCH |
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| series | ChemistryEurope |
| spelling | doaj-art-5e0a96c75dd64d80b6485194af15a8462025-01-13T07:31:32ZengWiley-VCHChemistryEurope2751-47652025-01-0131n/an/a10.1002/ceur.202400061(Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicalsDr. Moritz Scharnhölz0Dr. Jose Juan Gamboa Carballo1Dr. Nils Trapp2Dr. Rene Verel3Dr. Peter Coburger4Prof. Dr. Hansjörg Grützmacher5Department of Chemistry and Applied Biosciences ETH Zürich Vladimir-Prelog-Weg 1 8093 Zürich SwitzerlandDepartment of Chemistry and Applied Biosciences ETH Zürich Vladimir-Prelog-Weg 1 8093 Zürich SwitzerlandDepartment of Chemistry and Applied Biosciences ETH Zürich Vladimir-Prelog-Weg 1 8093 Zürich SwitzerlandDepartment of Chemistry and Applied Biosciences ETH Zürich Vladimir-Prelog-Weg 1 8093 Zürich SwitzerlandDepartment of Inorganic Chemistry TU München Lichtenbergstraße 4 85747 Garching GermanyDepartment of Chemistry and Applied Biosciences ETH Zürich Vladimir-Prelog-Weg 1 8093 Zürich SwitzerlandAbstract Dehalogenation of (PBr)2C2(PPh3)2 with potassium graphite, KC8, leads to Cs‐P4C4(PPh3)4, which can be viewed as a PPh3 adduct of a Cs‐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 Cs‐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 Cs‐P4C4(PR3)4 is a one‐step process.https://doi.org/10.1002/ceur.202400061Cage compoundsCoordination ChemistryPhosphorus HeterocyclesQuantum ChemistryRadicals |
| spellingShingle | Dr. Moritz Scharnhölz Dr. Jose Juan Gamboa Carballo Dr. Nils Trapp Dr. Rene Verel Dr. Peter Coburger Prof. Dr. Hansjörg Grützmacher (Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals ChemistryEurope Cage compounds Coordination Chemistry Phosphorus Heterocycles Quantum Chemistry Radicals |
| title | (Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals |
| title_full | (Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals |
| title_fullStr | (Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals |
| title_full_unstemmed | (Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals |
| title_short | (Ph3P)4C4P4: Effect of substitution on the Oligomerization of carbon phosphide radicals |
| title_sort | ph3p 4c4p4 effect of substitution on the oligomerization of carbon phosphide radicals |
| topic | Cage compounds Coordination Chemistry Phosphorus Heterocycles Quantum Chemistry Radicals |
| url | https://doi.org/10.1002/ceur.202400061 |
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