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Crystalline Germanium-Dipyrromethene Radicals:from a Delocalized Neutral to a Localized Cation

Chinese Journal of Chemistry 2022年第20期40卷 2387-2392页

作者： Yuyang Dai Manling Bao Wenjuan Wang Zhuofeng Xie Chunmeng Liu Yuanting Su College of Chemistry Chemical Engineering and Materials ScienceSchool of Radiation Medicine and ProtectionSoochow UniversitySuzhouJiangsu215123 China State Key Laboratory of Coordination Chemistry Nanjing UniversityNanjingJiangsu210023 China

Both dipyrromethene complexes and radicals of heavier main group elements have been of high interest.However,cationic germanium radicals and dipyrromethene-based radicals of heavier main group elements are still escaped to be isolated.Herein,we report the isolation and full characterization of a neutral Ge(I)-masked dipyrromethene-based radical 3 and the first cationic Ge(III)-centered radical 5^(·+)as stable crystalline solids.3 behaves as a germanium(I)radical in its reaction with diphenyl disulfide to form the Ge-S bond,although X-ray crystallographic,EPR spectroscopic,computational studies revealed that the unpaired electron of 3 is mainly delocalized over the C_(9)N_(2)Ge backbone and the allylic radical character is also significant in 3.In contrast to 3,the spin density of 5^(·+)is mainly localized at the Ge center with minor contribution from the dipyrromethene ligand.Moreover,reduction of 5^(·+)with potassium graphite quantitatively regenerates 5,illustrating a reversible one-electron redox pair.

关键词： Radicals main group element Germanium Dipyrromethene X-ray diffraction

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Carbon-halogen bond activation by a structurally constrained phosphorus(Ⅲ)platform

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Chinese Chemical Letters 2021年第4期32卷 1432-1436页

作者： Penglong Wang Qin Zhu Yi Wang Guixiang Zeng Jun Zhu Congqing Zhu State Key Laboratory of Coordination Chemistry Jiangsu Key Laboratory of Advanced Organic MaterialsSchool of Chemistry and Chemical EngineeringNanjing UniversityNanjing 210093China Kuang Yarning Honors School Institute for Brain SciencesNanjing UniversityNanjing 210093China State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials(iChEM) and Department of ChemistryCollege of Chemistry and Chemical EngineeringXiamen UniversityXiamen 361005China

Theσ-bond activation by main group element has received enormous attention from theoretical and experimental chemists.Here,the reaction of C-X(X=Cl,Br,I)bonds in benzyl and allyl halides with a pincer-type phosphorus(Ⅲ)species was reported.A series of structurally robust phosphorus(Ⅴ)compounds were formed via the formal oxidative addition reactions of C-X bonds to the phosphorus(Ⅲ)center.Density functional theory calculations show that the nucleophilic addition process is more favorable than the direct oxidative addition mechanism.Isomerization of bent structures of phosphorus(Ⅲ)compound to poorly nucleophilic compounds to undergo further C-X bond activation can be rationalized by frontier molecule orbital analysis.This study not only provides a deep understanding of the reactivity of phosphorus(Ⅲ)species but also demonstrates a potential of main group elements for the small-molecule activation.

关键词： Pincer ligand Phosphorus C-X bond activation main group element

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