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 

机构地区：[1]Beijing National Laboratory for Molecular Sciences(BNLMS),State Key Laboratory for Structural Chemistry of Unstable and Stable Species,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China [2]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Science China Chemistry》2022年第8期1594-1600,共7页中国科学（化学英文版）

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)。

摘　　要：Exploring metal cluster reactivity with alkyl halides enables to understand the related chemical mechanism of metal surfaces in terms of active sites.Here 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 spectrometer.Strong 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)^(+)products.Interestingly,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,respectively.Also 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.

关 键 词：metal cluster superatom HALIDE superatomic complex gas-phase reaction 

分 类 号：O641.4[理学—物理化学]