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

• Published in: Russian journal of coordination chemistry 2023-11, Vol.49 (11), p.743-752
• Main Authors: Vikulova, E. S., Il’in, I. Yu, Sukhikh, T. S., Artamonova, P. K., Morozova, N. B.
• Format: Article
• Language: English
• Subjects: Benzene; Chemical analysis; Chemical vapor deposition; Chemistry; Chemistry and Materials Science; Crystallization; Infrared spectroscopy; Inorganic Chemistry; Ligands; NMR spectroscopy; Physical Chemistry; Silver; Thermodynamic properties; Thermogravimetry; X-ray diffraction
• ISSN: 1070-3284; 1608-3318
• DOI: 10.1134/S1070328423600407

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 [Ag 4 (C 6 H 6 ) 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 μ 2 -κ 1 (O):κ 1 (O') function of the Ofhac ligands (Ag–O, 2.458(2)–2.461(2) Å), while COD is κ 2 -η 2 :η 2 -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.