Tiara-like Octanuclear Palladium(II) and Platinum(II) Thiolates and Their Inclusion Complexes with Dihalo- or Iodoalkanes

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• 作者：Yukari Yamashina ; Yasutaka Kataoka ; Yasuyuki Ura
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：April 7, 2014
• 年：2014
• 卷：53
• 期：7
• 页码：3558-3567
• 全文大小：584K
• 年卷期：v.53,no.7(April 7, 2014)
• ISSN：1520-510X

文摘

A tiara-like octanuclear palladium thiolate complex, [Pd(渭-SCH₂CO₂Me)₂]₈, that has a toroidal structure was synthesized via reactions of either PdCl₂ with methyl thioglycolate/N,N-diisopropylethylamine (DIEA) (conventional method) or [PdCl₂(MeCN)₂] with m-C₆H₄(CMe₂SCH₂CO₂Me)₂ (alternative method). In the latter method, the tiara-like complex formed via the corresponding SCS-pincer complex and/or 1:1 PdCl₂ and ligand complexes. With respect to the platinum analogues, the alternative method efficiently produced the tiara-like octanuclear complex [Pt(渭-SCH₂CO₂Me)₂]₈ in high purity. Small molecules, such as CH₂Cl₂, ClCH₂CH₂Cl, CH₂Br₂, and CH₃I, were accommodated in the inner voids of the tiara rings to form 1:1 inclusion complexes. These complexes are stabilized not only by weak CH路路路X hydrogen bonds (X = Cl or Br) between the methylene protons of four or eight axially positioned methoxycarbonylmethyl groups on the tiara rings and the halogen atoms of the guest molecules but also by weak coordination of the halogen atoms to the transition-metal atoms.