Abstract

Two new Ag(I) complexes with 1,1,1,5,5,6,6,6-octafluorohexane-2,4-dionate ion (Ofhac) and π‑donor neutral ligands, vinyltriethylsilane (VTES) or cycloocta-1,5-diene (COD), were synthesized with the goal to expand the library of silver precursors for chemical vapor deposition. The products were characterized by elemental analysis and IR and NMR spectroscopy. The complex [Ag(VTES)(Ofhac)] (I) was liquid under standard conditions; the temperature of its crystallization was below –20°C. Treatment of I with benzene gave rise to crystals of [Ag₄(C₆H₆)₂(Ofhac)₄]_∞ (II), which was confirmed by NMR and X-ray diffraction (CCDC no. 2232810). The structure of [Ag(COD)(Ofhac)]₂ (III) was established by X-ray diffraction (CCDC no. 2232809). The binuclear molecules are formed due to the μ₂-κ¹(O):κ¹(O') function of the Ofhac ligands (Ag–O, 2.458(2)–2.461(2) Å), while COD is κ²-η²:η²-coordinated (Ag–C, 2.420(17)–2.684(11) Å). The thermal properties of I and III in comparison with analogues containing 1,1,1,5,5,5-hexafluoropentane-2,4-dionate ion (Hfac) were studied by thermogravimetry.

中文翻译：

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1,1,1,5,5,6,6,6-八氟己烷-2,4-二酸银与 π-供体配体的配合物：合成、结构和热性质

摘要

两种新型 Ag(I) 配合物，含有 1,1,1,5,5,6,6,6-八氟己烷-2,4-二酸根离子 (Ofhac) 和 π 供体中性配体、乙烯基三乙基硅烷 (VTES) 或 cycloocta-1合成了 ,5-二烯 (COD)，目的是扩大用于化学气相沉积的银前体库。通过元素分析、红外光谱和核磁共振光谱对产物进行了表征。复合物 [Ag(VTES)(Ofhac)] ( I ) 在标准条件下为液体；其结晶温度低于–20°C。用苯处理I产生[Ag ₄ (C ₆ H ₆ ) ₂ (Ofhac) ₄ ] _∞ ( II )晶体，这通过NMR和X射线衍射证实(CCDC no.2232810)。_{[Ag(COD)(Ofhac)] 2} ( III )的结构通过X射线衍射确定（CCDC no. 2232809）。双核分子的形成是由于Ofhac 配体 (Ag–O, 2.458(2)–2.461(2) Å) 的μ ₂ -κ ¹ (O):κ ^{1 (O') 功能，而 COD 是 κ 2} -η ² :η ²配位（Ag–C, 2.420(17)–2.684(11) Å）。通过热重分析研究了I和III的热性质，并与含有 1,1,1,5,5,5-六氟戊烷-2,4-二酸根离子 (Hfac) 的类似物进行了比较。