Synthesis, Characterization and Molecular Structures of Yttrium Trifluoroacetate Complexes with O‐ and N‐Donors: Complexation vs. Hydrolysis

Abstract

Dehydration and complexation reactions of [Y(TFA)3(H2O)3] (1; TFA = O2CCF3) were investigated with O‐ and N‐donor ligands in order to obtain suitable precursors for MOD (Metal Organic Deposition). Anhydrous adducts such as [Y2(μ,η2‐TFA)4(η1‐TFA)2(OHC2H4OiPr)4] (3), [Y2(μ,η2‐TFA)4(η1‐TFA)2(OHC2H4OC2H4OMe)2] (4), or [Y(TFA)3(triglyme)] (5) were isolated. The reactions with N‐donor ligands are more complex and afford mixed‐ligand derivatives such as [Y(TFA)3(H2O)2(LL)]m [LL = TMEDA (9), Me2NC2H4NMeC2H4NMe2 (10)] and, in the case of primary amines, yttrium oxohydroxo derivatives such as [H3O][Y3(μ3‐OH)(μ‐O)3(η1‐TFA)3(H2O)6(en)3] (6; en = NH2C2H4NH2). All complexes were characterized by elemental analysis, FT‐IR, and by single‐crystal X‐ray diffraction for 3, 4, and 6. All structurally characterized complexes contain on eight‐coordinate Y centers. Perfluorobutyrate and difluoroacetate derivatives were also prepared. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Solution design for low-fluorine trifluoroacetate route to YBa2Cu3O7films

“…The FTIR spectrum accounts for the presence of TFA ligands in different bonding modes, most notably a strong broad absorption in the 1732-1622 cm -1 region centered at 1685 cm -1 and strong absorptions centered at 1208 cm -1 and 1150 cm -1 [32][33][34][35] [36]. In addition, a broad band in the 3050-3700 cm -1 region centered at 3433 cm -1 is related to water [32][33][34]. FTIR spectra show a progressive diminution of the absorption peaks related to propionate groups from 200ºC up to 300ºC while TFA absorption peaks remain unaffected up to 300ºC, and at 320ºC there is a significant diminution of the amplitude of TFA absorption peaks.…”

The Interplay between Yttrium and Barium or Copper Trifluoroacetates and N‐Methyldiethanolamine: Synthesis of a Heterometallic Y3Cu Trifluoroacetate Complex and a Homometallic Ba‐TFA 1D Polymer

“…Trifluoroacetic acid (TFAH) was stored over molecular sieves. [Ba(TFA) 2 ], [Cu(TFA) 2 (MeOH)] [12,13] and [Y(TFA) 3 (H 2 O) 3 ] [14] were prepared as reported previously. Analytical data were obtained from the Service Central dЈAnalyses du CNRS.…”

“…[12][13][14] The low-frequency absorptions at 632-404 cm -1 are due to the ν(M-O) and ν(M-N) vibrations. [12][13][14] The 1 H NMR spectrum of 2 indicates the presence of protonated N-methyldiethanolamine ligands in at least two different environments. It exhibits a broad peak at δ = 5.30 ppm, two triplets (J = 6.0 Hz) at δ = 3.85 and 3.75 ppm, two broad peaks at δ = 2.82 and 2.53 ppm and a singlet at δ = 1.86 ppm due to OH, OCH 2 , NCH 2 and NMe groups, respectively.…”

“…[8] The distance between one TFA counteranion (O41) and the oxygen of the µ 3 -hydroxo group O1M3···O41 is 2.802(6) Å, which suggests hydrogen bonding. The µ 3 -OH must originate from the coordinated water of [Y(TFA) 3 [14] The structure of 2 is that of a homometallic Ba 1D coordination polymer of formula [Ba 3 Figures 3 and 4). The triply bridging µ 3 -η 1 :η 2 :η 1 coordination mode is known for TFA (Scheme 2) for a Ba [24] and few other complexes, [25] but no secondary F···cation bond has been reported so far.…”

“…[12][13][14] The 1D coordination polymer [Ba 3 Cu 2 (µ,η 2 -TFA) 6 (µ,η 2 -dmea) 4 (MeOH) 2 ·2MeOH] 1ϱ was recently reported by our lab from the reaction between copper powder and [Ba(TFA) 2 ] ϱ in methanol under air and in the presence of N-dimethylethanolamine (dmeaH). [12] The use of N-methyldiethanolamine (mdeaH 2 (2), respectively, which were characterised by X-ray diffraction and FT-IR, X-band ESR (for 1) and NMR (for 2) spectroscopy.…”