Complexes of Silver 1,1,1,5,5,6,6,6-Octafluorohexane-2,4-dionate with π-Donor Ligands: Synthesis, Structure, and Thermal Properties

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.