Ligand-mediated reactivity in CO oxidation of yttrium-nickel monoxide carbonyl complexes

• Published in: Chinese chemical letters 2025-01, Vol.36 (2), p.110278, Article 110278
• Main Authors: Zhang, Jumei, Zhang, Ziheng, Li, Gang, Qiao, Hongjin, Xie, Hua, Jiang, Ling
• Format: Article
• Language: English
• Subjects: CO oxidation; Electron donor; Heteronuclear cluster; Photoelectron velocity-map imaging spectroscopy; Quantum chemical calculation
• ISSN: 1001-8417
• DOI: 10.1016/j.cclet.2024.110278

A series of heteronuclear yttrium-nickel monoxide carbonyl complexes YNiO(CO)n− (n = 1–5) were generated in a pulsed-laser vaporization source and characterized by mass-selected photoelectron velocity-map spectroscopy combined with theoretical calculations. CO ligand-mediated reactivity in CO oxidation of yttrium-nickel monoxide carbonyl complexes was experimentally and theoretically identified. During the consecutive CO adsorption, a μ2-O linear structure was most favorable for YNiO(CO)n− (n = 1, 2), then a structure in which the terminal O was bonded to the Y atom became favored for YNiO(CO)3−, and finally a structure bearing a CO2 moiety was most favorable for YNiO(CO)n− (n = 4, 5). Theoretical calculations indicated that the Ni atom acted as an electron acceptor and accumulated electron density at n ≤ 3, and then served as an electron donor along with the Y atom to contribute electron density in the rearrangement that accompanied CO oxidation at n > 3. [Display omitted] Photoelectron spectroscopic and theoretical studies reveal the geometric evolution of YNiO(CO)n− (n = 1–5).