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

• Published in: Chinese chemical letters Vol. 32; no. 4; pp. 1432 - 1436
• Main Authors: Wang, Penglong, Zhu, Qin, Wang, Yi, Zeng, Guixiang, Zhu, Jun, Zhu, Congqing
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.04.2021; State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China%State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China; State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China%Kuang Yaming Honors School, Institute for Brain Sciences, Nanjing University, Nanjing 210093, China%State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China; Kuang Yaming Honors School, Institute for Brain Sciences, Nanjing University, Nanjing 210093, China
• Subjects: C[sbnd]X bond activation; Main group element; Phosphorus; Pincer ligand; Pincer ligand; CX bond activation; Phosphorus; Main group element; C > X bond activation
• ISSN: 1001-8417; 1878-5964
• DOI: 10.1016/j.cclet.2020.11.005

The C–X bond activation by a pincer-type phosphorus platform was accomplished via an electrophilic addition rather than a direct oxidative addition to a structurally constrained phosphorus(III) center. This study further highlights the potential of main group elements in the activation of small molecules. [Display omitted] The σ-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.