Reactions on a 1,2‐Dicarbonyl Moiety of a Fullerene Skeleton
Reactions on a 1,2‐Dicarbonyl Moiety of a Fullerene Skeleton
复制标题
富勒烯骨架 1,2-二羰基部分的反应
DOI：
10.1002/chem.202100640
复制
发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Murata Yasujiro
中科院分区：
文献类型：
--
作者：
Hashikawa Yoshifumi;Li Jiayue;Okamoto Shu;Murata Yasujiro
开笼的富勒烯骨架上的1，2-二羰基是进一步衍生化的合适构件之一。在这里，我们讨论了1，2-二羰基化合物的化学转化为β-氧代-磷叶立德、酸酐和α-亚甲基羰基衍生物。尽管最后一个分子中具有空间上很小的亚甲基单元，但包裹的水分子的释放被显著抑制，而在P原子上含有三个基团的β-氧代-磷叶立德使插入/释放动力学更快，这意味着膦取代基的灵活性。用磷叶立德和亚甲基单元取代羰基在很大程度上改变了富勒烯骨架的电化学性质，这可能分别是由于整个分子上的阴离子电荷离域和一个电子可撤回的羰基的去除引起的。
A 1,2‐dicarbonyl moiety on a cage‐opened fullerene skeleton is one of suitable building blocks for the further derivatization. Herein, we discuss the chemical transformation of a 1,2‐dicarbonyl compound intoβ‐oxo‐phosphorus ylide, acid anhydride, andα‐methylene carbonyl derivatives. Despite possessing a sterically small methylene unit in the last one, the release of an encapsulated water molecule was significantly supressed whereas theβ‐oxo‐phosphorus ylide bearing three bulkyp‐tolyl groups on the P‐atom enabled the faster insertion/release dynamics, implying the flexibility of the phosphonium substituent. The replacement of the carbonyl group with phosphorus ylide and methylene units largely varied electrochemical properties of the fullerene skeleton, likely arising from the anionic charge delocalized over the entire molecule and removal of an electron‐withdrawable carbonyl group, respectively.