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用核磁共振的方法研究金属络合物分子间的动态交换反应,可以获得交换产物的核磁共振信号、立体化学信息及一些动力学、热力学数据,对了解交换机理及络合物的立体结构十分重要.Kairi等人曾用核磁共振方法研究了分子内及分子间的动态交换反应,取得了一些有意义的结果.本文在研究Ga(Ttfac)_3分子内动态交换反应的基础上,研究了Ga(Ttfac)_3/Ga(acac)_3体系分子间的配体交换反应(其中Ttfac为非对称二卤配体噻吩甲酰三氟丙酮C_4H_3S-CO-CH_2-CO-CF_3,acac为对称二卤配体乙酰丙酮CH_3-CO-CH_2-CO-CF_3).实验结果表明由交换反应产生了混合配体络合物,交换反应中各络合物平衡时的分布服从随机统计分布,求得了交换反应的平衡常数及焓变、熵变.兹将研究结果报道如下.
Using NMR to study the dynamic exchange reaction between metal complex molecules, the NMR signal, the stereochemical information and some kinetic and thermodynamic data of the exchange product can be obtained, which is very important for understanding the exchange mechanism and the three-dimensional structure of the complex .Kairi et al. Have studied the intramolecular and intermolecular dynamic exchange reactions by NMR and obtained some meaningful results.In this paper, based on the study of the dynamic exchange reaction of Ga (Ttfac) Ttfac) _3 / Ga (acac) _3 system, wherein Ttfac is an asymmetric dihalide ligand, thenoyltrifluoroacetone C_4H_3S-CO-CH_2-CO-CF_3 and acac is a symmetric dihalo ligand Acetylacetone CH_3-CO-CH_2-CO-CF_3) .Experimental results show that the mixed ligand complexes are produced by the exchange reaction. The equilibrium distribution of each complex in the exchange reaction follows a stochastic statistical distribution, and the equilibrium of the exchange reaction is obtained Constant and enthalpy change, entropy change. The results are reported below.