| 两个基于苯并噻唑-2-硫酮的银(Ⅰ)配合物的合成、晶体结构和光谱性质 |
| Syntheses, Crystal Structures and Spectroscopic Properties of Two Benzothiazoline-2-thione-Based Complexes for Silver(Ⅰ) |
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| 摘要: 合成了2个含有杂环硫酮的银(Ⅰ)配合物,[AgCl(PPh3)2(BTZT)]2 (1),[Ag(PPh3)2(BTZT)2](NO3)CH3OH (2)(PPh3=三苯基膦; BTZT=苯并噻唑-2-硫酮),并通过红外光谱、X射线单晶衍射、荧光光谱和核磁共振氢谱进行表征和分析。杂环硫酮存在化学活性基团-N(H)-C(=S)-,在平衡中与其硫醇形式可以相互转化。2个配合物是在含有2-巯基苯并噻唑(MBT)的甲醇与二氯甲烷混合溶液中,AgCl或AgNO3与三苯基膦反应得到的。配合物1的每个不对称单元中包含2个相同的分子结构,但是它们具有不同的键长和键角。配合物2是一个简单的单核杂配配合物,它的主体结构通过氢键作用连接游离的CH3OH和NO3-离子。配合物1和2发射峰的红移源于配体中的π-π*跃迁。 |
| 关键词: 银 三苯基膦 2-巯基苯并噻唑 苯并噻唑-2-硫酮 |
| 基金项目: 国家自然科学基金(No.21171119),863国家高技术研究发展计划(No.2012AA063201),北京教育委员会基金(No.KM201210028020),北京市优秀人才项目(No.2010D005016000002),北京市自然科学基金(No.7122015)资助项目。 |
| Abstract: Two silver(Ⅰ) complexes with heterocyclic thione, [AgCl(PPh3)2(BTZT)]2 (1) and [Ag(PPh3)2(BTZT)2](NO3)·CH3OH (2) (PPh3=triphenylphosphine; BTZT=benzothiazoline-2-thione) have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Heterocyclic thiones possess chemically active groups -N(H)-C(=S)- in equilibrium with its thiol form. 1 and 2 are obtained by the reactions of AgCl or AgNO3 with PPh3 in the presence of 2-mercaptobenzothiazole (MBT) in mixed solvent (CH3OH/CH2Cl2). The complex 1 contains two same structures in each asymmetric unit, but there are different bond lengths and bond angles. Complex 2 is a simple mono-nuclear heteroleptic complex whose main structure links free CH3OH and NO3- anion by hydrogen bonding interactions. The red-shift of emission peak of 1~2 is derived from ligand-centered π-π* transition. CCDC: 1059719, 1; 1059720, 2. |
| Keywords: silver triphenylphosphine 2-mercaptobenzothiazole benzothiazoline-2-thione |
| 投稿时间：2015-04-21 修订日期：2015-05-13 |
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| 李中峰,张彦茹,崔洋哲,耿文筱,刘敏,金琼花.两个基于苯并噻唑-2-硫酮的银(Ⅰ)配合物的合成、晶体结构和光谱性质[J].无机化学学报,2015,31(8):1637-1643. |
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