Citation: He-Lin WANG, Zhi-Liang GUO, Bo-Zhi LIU, Zhuang-Ze WU, Li-Xu LEI. Less solvent solid-state consecutive coordination reaction of copper chloride[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(8): 1536-1544. doi: 10.11862/CJIC.2023.093 shu

Less solvent solid-state consecutive coordination reaction of copper chloride

School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China

Corresponding author: Li-Xu LEI, lixu.lei@seu.edu.cn
Received Date: 16 January 2023
Revised Date: 23 April 2023

Figures(6)

The less solvent solid-state reaction (LSR) between CuCl₂·2H₂O and NH₄Cl in a little water produced only (NH₄)₂[CuCl₄(H₂O)₂] since NH₄[CuCl₃] was not stable in water; however, in a little absolute ethanol at 60 ℃, the LSR produced NH₄[CuCl₃], or (NH₄)₂[CuCl₄] according to the mixed stoichiometric ratio. The LSR of CuCl₂ and NH₄Cl in a 1∶2 molar ratio proceeds in two steps: the formation of NH₄[CuCl₃] at an early stage and a further reaction between NH₄[CuCl₃] and remaining NH₄Cl to form the final product (NH₄)₂[CuCl₄]. In contrast, the LSR of CuCl₂·2H₂O and 2, 2′-bipyridine (bipy) in 1∶1 molar ratio in a little water produced solely [Cu(bipy)Cl₂], but the 1∶2 product, [Cu(bipy)₂Cl₂]·2H₂O did appear in its early stage. The reason may be that the structure of the solid CuCl₂·2H₂O, which is polymerized planer trans-[CuCl₂(H₂O)₂], converts to molecular trans-[CuCl₂(H₂O)₄] in water, and the latter makes the activation energy of successive substitution of two H₂O molecules by bipy closer. Thus, bipy rapidly and successively replaces four water molecules in trans-[CuCl₂(H₂O)₄] to form a 1∶2 product. This surprising result indicates that the LSR of [Cu(bipy)₂Cl₂]·2H₂O and CuCl₂·2H₂O is also spontaneous, and according to thermodynamics, it is possible if the Δ_rG^⊖ of the second reaction is bigger than that of the first one of the consecutive reactions. Therefore, the LSR could also proceed stepwise, which is hard to find in solution reactions.
- less solvent solid-state reaction,
- consecutive reaction,
- stepwise reaction,
- X-ray diffraction,
- reaction of 100% yield
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