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 spectrosco...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.展开更多
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)。
文摘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.
