Isolated Carbon(I) Species Featuring a Carbone Cation Radical

报告时间：2026年1月23日（周五）下午16:00

报告地点：化学学科楼A408

个人简介

王朝谚Tiow-Gan Ong，无机化学家，以其通过“配体设计策略”进行的non-octet体化学键研究而闻名。曾任中国台湾“中央研究院”化学研究所研究员。于2025年9月加入香港中文大学（深圳）理工学院，成立“先进碳配体与金属主族催化实验室”。主要工作致力于通过配体设计策略探索化学键的本质与应用，为有机金属化学和催化科学的发展提供了重要启示，其成果在学术界和工业界均具有深远影响。近年作为通讯作者在Nature Chem.、Nat. Synth.、JACS、Angew. Chem. Int. Ed.等顶尖期刊上发表多篇论文，其研究成果推动了相关领域的发展。此外，他曾获得多项殊荣，包括渥太华大学访问研究奖（2020年）、台湾杰出研究奖（2019年）、中国台湾“中央研究院”杰出学者计划奖（2021年和2024年）及国家级人才项目（讲座教授 2025年）。

报告摘要：

Carbynes, characterized by their radical and carbene attributes, possess three non-bonding electrons and have garnered significant scientific interest. The high reactivity and complex hybridization of valence orbitals in carbynes have impeded the isolation of free carbon(I) species. Carbodicarbenes are divalent carbon (0) species with two electron lone-pairs, which are in principle capable of losing an electron to generate a radical cation carbon(I) species containing three non-bonded electrons,^[1-2] similar to the frontier orbital of a carbyne without a vacant orbital. Herein, we describe the isolation of a crystalline cation radical carbon(I), [1-CDC]^•+, prepared by a single electron transfer (SET) between a carbodicarbene and a nitro-aromatic compound to generate a stable radical ionic pair.^[3] Electron paramagnetic resonance (EPR) and X-ray crystallography with quantum chemical analysis show that the unpaired electron of [1-CDC]^•+ resides in the p(p) atomic orbital (AO) of the secondary carbon with some delocalization to the N-heterocyclic carbene (NHC) ligands. Exploring the reactivity of this carbon(I) radical cation revealed its capacity to mediate a variety of C-O and C-C cross-coupling reactions with electron-deficient aryl halides. These findings not only expand the understanding of carbon(I) radical chemistry but also open new avenues for radical methodologies in organic synthesis and catalysis.

Reference

1. Chen, W. C.; Shen, J. S.; Jurca, T.; Peng, C. J.; Lin, Y. H.; Wang, Y. P.; Shih, W. C.; Yap, G. P. A.; Ong, T. G*., Expanding the Ligand Framework Diversity of Carbodicarbenes and Direct Detection of Boron Activation in the Methylation of Amines with CO2. Angew. Chem.-Int. Edit. 2015, 54, 15207-15212.

2. Chen, W. C.; Hsu, Y. C.; Lee, C. Y.; Yap, G. P. A.; Ong, T. G*., Synthetic Modification of Acyclic Bent Allenes (Carbodicarbenes) and Further Studies on Their Structural Implications and Reactivities. Organometallics 2013, 32, 2435-2442.

3. Chan, Y.-C.; Xiao, H.-X.; Qin, L.; Shen, J.-S.; Yang, C.-R.; Yap, G. P. A.; Ching, W.-M.; Chen, W.-C*.; Chiang, Y.-W*.; Frenking, G*.; Zhao*, L.; Ong, T.-G*. Isolated Carbon(I) Species Featuring a Carbone Cation Radical. Nat. Synth. 2025, in press.