title: The unique liquid chromatographic properties of Group 11 transition metals for the separation of unsaturated organic compounds.
abstract: Silver(I) and copper(I) are known to form reversible complexes with π bonds, which have been exploited in LC for separating unsaturated organic compounds. Prominent examples include the use of AgNO3-impregnated silica gel in LC, and the use of copper(I) salts for selective extraction of alkenes from hydrocarbon mixtures. The Dewar-Chatt-Duncanson model is often invoked to explain the interaction between Ag(I) and Cu(I) and π bonds. However, it is unclear if such a reversible interaction is directly related to their d(10) outer electronic configurations. Particularly, Au(I) has not been reported to separate olefins with different numbers of double bonds in LC. Also, there has not been a systematic comparison of the liquid chromatographic properties of other d(10) transition metal salts (e.g., Zn(II), Cd(II)), making it difficult to fully understand the observed reversible interactions of Ag(I) and Cu(I) with π bonds. We demonstrate for the first time that silica gel impregnated with all three Group 11 transition metals with 1+ oxidation state strongly and similarly retain olefin compounds in LC, while transition metals from Groups 10 and 12 do not. We also tested a range of functionalized silica gels to improve the stability of Cu(I) and Au(I) ions on the surface of the silica.
authors.affiliation: Department of Geological Sciences, Brown University, Providence, RI, USA.
authors.forename: José C
authors.initials: JC
authors.lastname: Aponte
authors.forename: James T
authors.initials: JT
authors.lastname: Dillon
authors.forename: Yongsong
authors.initials: Y
authors.lastname: Huang
keywords: Compexation chromatography; Olefin separation; Silver thiolate chromatographic material; Transition metal complexes; pi bonds