Binding of carbon monoxide at a single nickel center and its oxidative reactivity toward CO2 and O2. (21st December 2021)

• Record Type: Journal Article
• Authors: Lee, Kunwoo; Choi, Jonghoon; Graham, Peter M.; Lee, Yunho
• Is Part Of: Bulletin of the Korean Chemical Society. Volume 43:Number 2(2022)
• Page Start: 222
• Page End: 226
• Publication Date: 2021-12-21
• Subjects: CODH -- nickel‐carbonyl -- reactivity toward CO2 and O2; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/bkcs.12452
• Languages: English
• ISSNs: 0253-2964

Abstract

Abstract: A nickel(0) monocarbonyl complex (1‐CO ) supported by a neutral tridentate PP2 ligand reveals significant stability toward CO2, which is clearly different from its analogous nickel monocarbonyl species supported by an anionic PNP ligand. Although both nickel(0)‐CO species possess a similar distorted tetrahedral geometry, the nickel site in 1‐CO is well protected by three phosphorus donors, while (NP2 )Ni(CO) possesses a nickel center having a site trans to the amide donor for effective CO2 binding. The current study shows that the structural preference of a tridentate ligand dictates nickel's reactivity toward CO2 . Its oxygenation by O2 (g) results in the formation of a nickel(II) carbonate species, which is followed by generating phosphine oxide. Abstract : A tetrahedral nickel(0) monocarbonyl complex reveals selective reactivity toward CO2 and O2, suggesting the structural preference of a tridentate ligand toward square planar or tetrahedral geometry is crucial for determining the reaction thermodynamics.