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

• Published in: Chinese chemical letters Vol. 34; no. 6; pp. 107702 - 571
• Main Authors: Yang, Jianpeng, Zhang, Jumei, Du, Shihu, Li, Gang, Zou, Jinghan, Jing, Qiangshan, Xie, Hua, Jiang, Ling
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.06.2023; School of Life Science,Ludong University,Yantai 264025,China%State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China; College of Chemistry and Chemical Engineering,Xinyang Normal University,Xinyang 464000,China%State Key Laboratory of Molecular Reaction Dynamics,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China
• Subjects: CO activation; Heteronuclear cluster; Photoelectron imaging; Quantum chemical calculations; Transition metal carbonyl; Heteronuclear cluster; Quantum chemical calculations; Photoelectron imaging; Transition metal carbonyl; CO activation
• ISSN: 1001-8417; 1878-5964
• DOI: 10.1016/j.cclet.2022.07.045

A series of heterotrinuclear Ti2Ni(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 CO 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. The CO activation by metal clusters plays an essential role in various areas, such as catalysis and organometallic synthesis. Photoelectron velocity-map imaging spectroscopy of heterotrinuclear Ti2Ni(CO)n– carbonyls reveals the capability of simultaneously accommodating the terminal, bridging, and side-on bonding modes, pointing to the weak, moderate, high C−O bond activation. [Display omitted]