Ligand accommodation causes altered reactivity of silver clusters with iodomethane:superatomic stability of Ag_(9)I_(2)^(+)in mimicking XeF_(2)

作     者：Haiming Wu Mengzhou Yang Benben Huang Wen Gan Zhixun Luo 

作者机构：Beijing National Laboratory for Molecular Sciences(BNLMS)State Key Laboratory for Structural Chemistry of Unstable and Stable SpeciesInstitute of ChemistryChinese Academy of SciencesBeijing 100190China University of Chinese Academy of SciencesBeijing 100049China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2022年第65卷第8期

页      面：1594-1600页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the Ministry of Science and Technology of China(2020YFA0714602) the National Natural Science Foundation of China(21722308,22003072) CAS Instrument Development Project(Y5294512C1) 

主　　题：metal cluster superatom halide superatomic complex gas-phase reaction 

摘      要：Exploring metal cluster reactivity with alkyl halides enables to understand the related chemical mechanism of metal surfaces in terms of active *** we report a study of Ag_(n)^(+)(n=1-27)clusters reacting with iodomethane by a flow tube apparatus in tandem with a customized triple quadrupole mass *** even/odd alternation of the Ag_(n)^(+)is observed in their reactions with CH_(3)I,where silver clusters with even-number,Ag_(2n)^(+),find favorable products of Ag_(2n)I_(1,3)^(+)series,while the Ag_(2n−1)^(+)clusters form Ag_(2n−1)I_(2,4)^(+)***,Ag_(9)^(+)shows up with prominent mass abundance but allows for the formation of Ag_(9)I_(2)^(+),which finds an echo with the formation of Ag_(10)I_(3)^(+).We illustrate the enhanced stability of Ag_(9)I_(2)^(+)and Ag_(10)I_(3)^(+)by showing their significantly enlarged highest occupied molecular orbital(HOMO)-lowest unoccupied molecular orbital(LUMO)gaps and balanced charge distribution compared with the bare metal clusters,*** elucidated,is the superatomic nature of these bare and iodinated silver clusters,especially Ag_(9)I_(2)^(+)which mimics the rare-gas compound XeF_(2).This study expands a vivid example of special and general superatoms,and enriches the general knowledge on how a ligand stabilizes a metal cluster.