Low Heat of Adsorption of Ethylene Achieved by Major Solid‐State Structural Rearrangement of a Discrete Copper(I) Complex. Issue 50 (15th November 2018)

• Record Type: Journal Article
• Authors: Jayaratna, Naleen B.; Cowan, Matthew G.; Parasar, Devaborniny; Funke, Hans H.; Reibenspies, Joseph; Mykhailiuk, Pavel K.; Artamonov, Oleksii; Noble, Richard D.; Dias, H. V. Rasika
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 50(2018)
• Page Start: 16442
• Page End: 16446
• Publication Date: 2018-11-15
• Subjects: chemisorption -- coordination chemistry -- copper -- olefin purification -- X-ray diffraction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201810460
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The trinuclear copper(I) pyrazolate complex [Cu3 ] rearranges to the dinuclear analogue [Cu2 ⋅(C2 H4 )2 ] when exposed to ethylene gas. Remarkably, the [Cu3 ]↔[Cu2 ⋅(C2 H4 )2 ] rearrangement occurs reversibly in the solid state. Furthermore, this transformation emulates solution chemistry. The bond‐making and breaking processes associated with the rearrangement in the solid‐state result in an observed heat of adsorption (−13±1 kJ mol −1 per Cu–C2 H4 interaction) significantly lower than other Cu–C2 H4 interactions (≥−24 kJ mol −1 ). The low overall heat of adsorption, "step" isotherms, high ethylene capacity (2.76 mmol g −1 ; 7.6 wt % at 293 K), and high ethylene/ethane selectivity (136:1 at 293 K) make [Cu3 ] an interesting basis for the rational design of materials for low‐energy ethylene/ethane separations. Abstract : Three's a crowd : A polyfluorinated, trinuclear copper complex absorbs ethylene and undergoes a major structural rearrangement leading to a dinuclear copper–ethylene complex. Upon removal of ethylene it reverts back to the trinuclear species. This process occurs both in solution and in the solid state.