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• W2354050906 endingPage "8546" @default.
• W2354050906 startingPage "8536" @default.
• W2354050906 abstract "This work reports the syntheses and the first crystal structures of the cationic carbone adducts [FC(PPh3)2]+ and [BrC(PPh3)2]+ and the protonated dication [FC(H)(PPh3)2]2+, which are derived from the carbone C(PPh3)2. Quantum chemical calculations and bonding analyses were carried out for the series of cations [AC(PPh3)2]+ and dications [AC(H)(PPh3)2]2+, where A=H, Me, F, Cl, Br, I. The bonding analysis suggests that the cations are best described as phosphane complexes L→(CA)+←L (L=PPh3), which are related to the neutral borylene adducts L→(BA)←L (L=cyclic carbene; A=H, aryl) that were recently isolated. The carbone adducts [AC(PPh3)2]+ possess a π electron lone pair at carbon and they can easily be protonated to the dications [AC(H)(PPh3)2]2+. The calculations of the dications indicate that the molecules are best represented as complexes L→(CHA)2+←L (L=PPh3) where a carbene dication is stabilized by the ligands. The central carbon atom in the cations and even in the dications carries a negative partial charge, which is larger than the negative charge at fluorine. There is also the peculiar situation in which the carbon–fluorine bonds in [FC(PPh3)2]+ and [FC(H)(PPh3)2]2+ exhibit the expected polarity with the negative end at fluorine, but the carbon atom has a larger negative charge than fluorine. Given the similarity of carbodiphosphorane C(PPh3)2 and carbodicarbene C(NHC)2, we expect that analogous compounds [AC(NHC)2]+ and [AC(H)(NHC)2]2+ with similar features as [AC(PPh3)2]+ and [AC(H)(PPh3)2]2+ can be isolated." @default.
• W2354050906 created "2016-06-24" @default.
• W2354050906 creator A5026160903 @default.
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• W2354050906 creator A5039534982 @default.
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• W2354050906 creator A5062167654 @default.
• W2354050906 date "2016-05-11" @default.
• W2354050906 modified "2023-10-07" @default.
• W2354050906 title "Proton Affinities of Cationic Carbone Adducts [AC(PPh₃)₂]⁺(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh₃)₂]²⁺" @default.
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• W2354050906 doi "https://doi.org/10.1002/chem.201600525" @default.

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