A Distinctive Pattern for Substituent Effects on Transition Metal Centers:Enhanced Electron-Donating Capacity of Cationic Palladium Species
作者机构：Department of ChemistryTsinghua UniversityBeijing 100084 College of ChemistryNankai UniversityTianjin 300071 Haihe Laboratory of Sustainable Chemical TransformationsTianjin 300192
出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)
年 卷 期：2023年第5卷第5期
页 面：1163-1175页
核心收录：
学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学]
基 金：provided by the National Natural Science Foundation of China(nos.21973052,21933008) the Young Elite Scientists Sponsorship Program by CAST(no.2019QNRC001),and the Haihe Laboratory of Sustainable Chemical Transformations
主 题：bond dissociation energy substituent effects palladium complexes thermodynamics structure–reactivity relationship
摘 要：Electronic and bonding situations at reaction centers are often detected by the remote substituent *** nonorganometallic reactions,this effect is conventionally described by the well-known Hammett-type substituent ***,for most transition metal(TM)-involved systems,no analogous numeral descriptors reflecting the intrinsic differences between metallic and nonmetallic bonding have been rigorously established till ***,we report a Pd(II)–O bond heterolysis energyΔG_(het)(Pd–O)study of the archetypal palladium complexes to represent the thermodynamics of the essential bond-breaking step in Pd-mediated *** we furnish the new substituent constantsσPd^(+)s and therefrom facilitate linear free-energy relationship(LFER)analysis for Pd-catalyzed ***,this led us to find an unexpected electron-donating ability of Pd(II)cation,which provided a gifted experimental support,with the aid of computation,to attribute the frustrating observation of a much scattered curvature in theΔG_(het)(Pd–O)-σ+correlation to the electrondonating capacity of the cationic palladium through back-donation of its *** of LFER analysis withσPd^(+)to predict the redox behavior of the palladium complex and in a kinetics *** study of transmetalation added further credence to their applicability to TM systems.
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