Biradicaloid and Zwitterion Reactivity of Dicarbondiphosphide Stabilized with N-Heterocyclic Carbenes
Biradicaloid and Zwitterion Reactivity of Dicarbondiphosphide Stabilized with N-Heterocyclic Carbenes
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N-杂环卡宾稳定的二碳二磷化物的双自由基和两性离子反应性
DOI：
10.1002/chem.201705403
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Chen Xiaodan
中科院分区：
文献类型：
--
作者：
Li Zhongshu;Hou Yuanfeng;Li Yaqi;Hinz Alex;er;Chen Xiaodan
在标准的实验室条件下，有机双自由基通常是寿命很短的物种，这使得它们的实验研究变得困难。相反，这些双自由基的杂原子取代的类似物由于π电子离域而表现出更高的稳定性，这就是为什么典型的杂环丁二基的主要基团双自由基(或双自由基)被深入研究的原因。本文利用N-杂环卡宾稳定的(L2)C_2P_2(L=N_2P_2)二碳二膦化合物来激活小分子中的单键和多键，其协同机理是可行的。这种反应活性可以通过二碳二磷酸盐化合物相当大的双自由基特性来解释，这一点得到了理论研究的进一步证实。此外，二碳二磷化物化合物还表现出对Lewis酸的Lewis碱性质，如硼烷和金属卤化物。
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.