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硫代酰肼和硫代二胺的有机锡(IV)配合物:合成、光谱及热学研究

Organotin(IV) complexes of thiohydrazides and thiodiamines: synthesis, spectral and thermal studies.

作者信息

Singh Rajeev, Kaushik N K

机构信息

Organometallic Chemistry Laboratory, Department of Chemistry, University of Delhi, Delhi 110007, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2006 Nov;65(3-4):950-4. doi: 10.1016/j.saa.2006.01.040. Epub 2006 May 3.

Abstract

Organotin(IV) complexes of tribenzyltin(IV) chloride and di(para-chlorobenzyl)tin(IV) dichloride with thiohydrazides have been reported. The ligands synthesized were bidentate coordinating through sulphur and terminal nitrogen atoms. These form 1:1 metal-ligand complexes. The following organotin(IV) complexes have been synthesized: (C(6)H(5)CH(2))(3)Sn(L(1))Cl, (p-ClC(6)H(4)CH(2))(2)Sn(L(1))Cl(2), (C(6)H(5)CH(2))(3)Sn(L(1))Cl, (p-ClC(6)H(4)CH(2))(2)Sn(L(2))Cl(2), (C(6)H(5)CH(2))(3)Sn(L(3))Cl, (p-ClC(6)H(4)CH(2))(2)Sn(L(3))Cl(2), where (L(1)): 2-phenylethyl N-thiohydrazide, (L(2)): N-(2-phenylethyl-N-thio)-1,3-propane diamine, (L(3)): N-(2-phenylethyl-N-thio)-1,2-ethane diamine. The complexes were synthesized by directly mixing, refluxing and stirring the ligands with organotin(IV) chlorides in a suitable solvent. The complexes were found to be pure and were characterized by elemental analysis, electronic, infrared, (1)H and (13)C NMR spectroscopy. These complexes were also studied for their thermal decomposition by thermogravimetry (TG) and differential thermal analysis (DTA). Various kinetic and thermodynamic parameters, viz. activation energy (E(a)), order of reaction (n), apparent activation entropy (S(#)) and heat of reaction (DeltaH) have been determined by using Horowitz-Metzger method. It was observed that these complexes are highly stable and the thermal degradation of these complexes is a spontaneous process. The ligands and their tin complexes have also been screened for their fungitoxicity activity and found to be quite active in this respect.

摘要

已报道了三苄基氯化锡(IV)和二(对氯苄基)二氯化锡(IV)与硫代酰肼形成的有机锡(IV)配合物。合成的配体通过硫原子和末端氮原子进行双齿配位。这些形成1:1的金属-配体配合物。已合成了以下有机锡(IV)配合物:(C₆H₅CH₂)₃Sn(L₁)Cl、(p-ClC₆H₄CH₂)₂Sn(L₁)Cl₂、(C₆H₅CH₂)₃Sn(L₁)Cl、(p-ClC₆H₄CH₂)₂Sn(L₂)Cl₂、(C₆H₅CH₂)₃Sn(L₃)Cl、(p-ClC₆H₄CH₂)₂Sn(L₃)Cl₂,其中(L₁):2-苯乙基N-硫代酰肼,(L₂):N-(2-苯乙基-N-硫代)-1,3-丙二胺,(L₃):N-(2-苯乙基-N-硫代)-1,2-乙二胺。通过在合适的溶剂中将配体与有机锡(IV)氯化物直接混合、回流和搅拌来合成配合物。发现这些配合物是纯的,并通过元素分析、电子光谱、红外光谱、¹H和¹³C NMR光谱进行了表征。还通过热重分析法(TG)和差示热分析法(DTA)研究了这些配合物的热分解。使用霍洛维茨-梅茨格方法确定了各种动力学和热力学参数,即活化能(Eₐ)、反应级数(n)、表观活化熵(S⁺)和反应热(ΔH)。观察到这些配合物非常稳定,并且这些配合物的热降解是一个自发过程。还对配体及其锡配合物的杀真菌活性进行了筛选,发现它们在这方面相当活跃。

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