Photoelectron imaging spectroscopic signatures of CO activation by the heterotrinuclear titanium-nickel clusters  

作　　者：Jianpeng Yang Jumei Zhang Shihu Du Gang Li Jinghan Zou Qiangshan Jing Hua Xie Ling Jiang 

机构地区：[1]College of Chemistry and Chemical Engineering,Xinyang Normal University,Xinyang 464000,China [2]State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [3]School of Life Science,Ludong University,Yantai 264025,China

出　　处：《Chinese Chemical Letters》2023年第6期567-571,共5页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.21873097,22103082,92061203,22125303 and 22288201);the Youth Innovation Promotion Association of the Chinese Academy of Sciences(CAS,No.2020187);the Strategic Priority Research Program of CAS(No.XDB17000000)。

摘　　要：A series of heterotrinuclear Ti_(2)Ni(CO)_(n)^(-)(n=6-9)carbonyls have been generated via a laser vaporization supersonic cluster source and characterized by mass-selected photoelectron velocity-map imaging spectroscopy.Quantum chemical calculations have been carried out to identify the structures and understand the experimental spectral features.The results indicate that a building block of Ti-Ti-Ni-C four-membered ring with the C atom bonded to Ti,Ti,and Ni is dominated in the n=6-8 complexes,whereas a structural motif of Ti-Ti-Ni triangle core is preferred in n=9.These complexes are found to be capable of simultaneously accommodating all the main modes of metal-CO coordination(i.e.,terminal,bridging,and side-on modes),where the corresponding mode points to the weak,moderate,high C-O bond activation,respectively.The number of CO ligands for a specific bonding mode varies with the cluster size.These findings have important implications for molecular-level understanding of the interaction of CO with alloy surfaces/interfaces and tuning the appropriate CO activation via the selection of different metals.

关 键 词：CO activation Transition metal carbonyl Heteronuclear cluster Photoelectron imaging Quantum chemical calculations 

分 类 号：O641.4[理学—物理化学] O657.3[理学—化学]