| 氯化铜的少溶剂固态连串配位化学反应 |
| Less solvent solid-state consecutive coordination reaction of copper chloride |
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| 摘要: 在少量水的存在下，由于NH4[CuCl3]对水不稳定，CuCl2·2H2O与氯化铵的配位化学反应只能得到1∶2产物(NH4)2[CuCl4(H2O)2]；但在无水乙醇中，无水CuCl2与氯化铵按1∶1或1∶2的物质的量之比混合时，能相应地得到NH4[CuCl3]或(NH4)2[CuCl4]。CuCl2·2H2O与2，2'-联吡啶(bipy)的少溶剂固态化学反应仍能像固态化学反应一样，根据反应物的配比生成相应的唯一产物，但在物质的量之比为1∶1的反应中发现1∶2产物曾经形成。热力学分析说明，如果连串反应的后一步的ΔrG⊖大于前一步的，则上述反应现象是可能的。 |
| 关键词: 少溶剂固态化学反应 连串反应 分步反应 X射线衍射 100%产率反应 |
| 基金项目: |
| Abstract: 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 ΔrG⊖ 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. |
| Keywords: less solvent solid-state reaction consecutive reaction stepwise reaction X-ray diffraction reaction of 100% yield |
| 投稿时间：2023-01-16 修订日期：2023-04-23 |
| 摘要点击次数: 1903 |
| 全文下载次数: 1058 |
| 王鹤霖,郭治良,刘柏志,吴庄泽,雷立旭.氯化铜的少溶剂固态连串配位化学反应[J].无机化学学报,2023,39(8):1536-1544. |
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