Biradicaloid and Zwitterion Reactivity of Dicarbondiphosphide Stabilized with N‐Heterocyclic Carbenes

Organic biradicals are usually very short lived species under standard laboratory conditions, which makes their experimental studies difficult. In contrast, heteroatom‐substituted analogues of these biradicals show enhanced stability due to π‐electron delocalization, which is why main group biradica...

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Bibliographic Details
Published in:Chemistry : a European journal 2018-04, Vol.24 (19), p.4849-4855
Main Authors: Li, Zhongshu, Hou, Yuanfeng, Li, Yaqi, Hinz, Alexander, Chen, Xiaodan
Format: Article
Language:English
Subjects:
biradicaloids
Carbenes
carbon
Chemical bonds
Chemistry
Halides
Lewis base
phosphorus
phosphorus heterocycles
Zwitterions
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Summary:Organic biradicals are usually very short lived species under standard laboratory conditions, which makes their experimental studies difficult. In contrast, heteroatom‐substituted analogues of these biradicals show enhanced stability due to π‐electron delocalization, which is why main group biradicals (or biradicaloids) of archetypical heterocyclobutanediyls have been thoroughly investigated. Herein, N‐heterocyclic carbene (NHC)‐stabilized dicarbondiphosphide compounds of the type (L2)C2P2 (L=NHC) were utilized to activate both single and multiple bonds in small molecules with a feasible concerted mechanism. This reactivity is explicable by considerable biradicaloid character of the dicarbondiphosphide compounds, which is further corroborated by theoretical studies. Furthermore, the dicarbondiphosphide compounds also exhibited Lewis base properties towards Lewis acids, such as borane and metal halides. Dual nature: NHC‐stabilized dicarbondiphosphide NHC→(C2P2)←NHC (NHC=N‐heterocyclic carbene) have biradicaloid and zwitterionic resonance structures (see figure), and both biradicaloid and zwitterionic characteristics have been demonstrated experimentally and theoretically.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201705403