Approaches to Alkaline Earth Metal-Organic Chemical Vapor Deposition Precursors. Synthesis and Characterization of Barium Fluoro-β-ketoiminate Complexes Having Appended Polyether "Lariats"

Deborah A. Neumayer, John A. Belot, Richard L. Feezel, Charles Reedy, Charlotte L. Stern, Tobin J Marks, Louise M. Liable-Sands, Arnold L. Rheingold

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Abstract

The synthesis and characterization of a family of β-ketoimines derived from 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hfa) and the corresponding volatile barium β-keioiminate - polyether complexes having the general formula Ba[CF3COCHC(NR)CF3]2 where R = (CH2CH2O)2CH3, (CH2CH2O)2CH2CH3, and (CH2CH2O)3CH2CH3 is reported. These complexes can be transported in the vapor phase at 160 °C/0.05 Torr without decomposition. The β-ketoiminate ligands are synthesized by condensation of the appropriate amine-terminated poly(ethylene oxide)s with the trimethylsilyl enol ether derivative of hfa and converted to barium β-ketoiminate - polyether complexes by reaction with BaH2. The poly(ethylene oxide) amines are in turn synthesized by triphenylphosphine-mediated reduction of the corresponding poly(ethylene oxide) azides (synthesized via the tosylates) to afford the amines in good yields and analytical purity. The amines, β-ketoimines, and barium complexes were characterized by elemental analysis, 1H, 19F, and 13C NMR spectroscopy, mass spectroscopy, and thermogravimetric analysis. The eight-and ten-coordinate Ba2+ complexes having the formula Ba[CF3COCHC(NR)CF3]2 where R = (CH2CH2O)2CH2CH3 [C22H28N2F12O6Ba; space group = monoclinic, P21; a = 12.1175(2) Å, b = 14.9238(2) Å, c = 16.9767(3) Å, a = γ = 90°, β = 90.0840(10)°, Z = 4] and R = (CH2CH2O)3CH2CH3 [C26H36N2F12O8Ba; space group = triclinic, P1 (#2); a = 10.971(2) Å, b = 12.134(2) Å, c = 15.280(4) Å. α = 89.94(2)°, β = 110.00(2)°, γ = 116.75(2)°, Z=2] were characterized by single-crystal X-ray diffraction. Both analyses reveal monomeric structures with the β-ketoiminate ligands coordinated to the Ba2+ center through all available oxygen and nitrogen atoms. These complexes are substantially more volatile than Ba(2,2,6,6,-tetramethyl-3,5-heptanedionate)2 but less so than the most volatile Ba(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)2·polyether complexes.

Original languageEnglish
Pages (from-to)5625-5633
Number of pages9
JournalInorganic Chemistry
Volume37
Issue number21
Publication statusPublished - 1998

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Alkaline Earth Metals
Organic Chemicals
alkaline earth metals
Polyethers
Barium
barium
Amines
metalorganic chemical vapor deposition
Chemical vapor deposition
amines
ethylene oxide
Polyethylene oxides
synthesis
Ligands
ligands
Azides
Ether
nitrogen atoms
Nuclear magnetic resonance spectroscopy
Thermogravimetric analysis

ASJC Scopus subject areas

  • Inorganic Chemistry

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Approaches to Alkaline Earth Metal-Organic Chemical Vapor Deposition Precursors. Synthesis and Characterization of Barium Fluoro-β-ketoiminate Complexes Having Appended Polyether "Lariats". / Neumayer, Deborah A.; Belot, John A.; Feezel, Richard L.; Reedy, Charles; Stern, Charlotte L.; Marks, Tobin J; Liable-Sands, Louise M.; Rheingold, Arnold L.

In: Inorganic Chemistry, Vol. 37, No. 21, 1998, p. 5625-5633.

Research output: Contribution to journalArticle

Neumayer, Deborah A. ; Belot, John A. ; Feezel, Richard L. ; Reedy, Charles ; Stern, Charlotte L. ; Marks, Tobin J ; Liable-Sands, Louise M. ; Rheingold, Arnold L. / Approaches to Alkaline Earth Metal-Organic Chemical Vapor Deposition Precursors. Synthesis and Characterization of Barium Fluoro-β-ketoiminate Complexes Having Appended Polyether "Lariats". In: Inorganic Chemistry. 1998 ; Vol. 37, No. 21. pp. 5625-5633.
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abstract = "The synthesis and characterization of a family of β-ketoimines derived from 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hfa) and the corresponding volatile barium β-keioiminate - polyether complexes having the general formula Ba[CF3COCHC(NR)CF3]2 where R = (CH2CH2O)2CH3, (CH2CH2O)2CH2CH3, and (CH2CH2O)3CH2CH3 is reported. These complexes can be transported in the vapor phase at 160 °C/0.05 Torr without decomposition. The β-ketoiminate ligands are synthesized by condensation of the appropriate amine-terminated poly(ethylene oxide)s with the trimethylsilyl enol ether derivative of hfa and converted to barium β-ketoiminate - polyether complexes by reaction with BaH2. The poly(ethylene oxide) amines are in turn synthesized by triphenylphosphine-mediated reduction of the corresponding poly(ethylene oxide) azides (synthesized via the tosylates) to afford the amines in good yields and analytical purity. The amines, β-ketoimines, and barium complexes were characterized by elemental analysis, 1H, 19F, and 13C NMR spectroscopy, mass spectroscopy, and thermogravimetric analysis. The eight-and ten-coordinate Ba2+ complexes having the formula Ba[CF3COCHC(NR)CF3]2 where R = (CH2CH2O)2CH2CH3 [C22H28N2F12O6Ba; space group = monoclinic, P21; a = 12.1175(2) {\AA}, b = 14.9238(2) {\AA}, c = 16.9767(3) {\AA}, a = γ = 90°, β = 90.0840(10)°, Z = 4] and R = (CH2CH2O)3CH2CH3 [C26H36N2F12O8Ba; space group = triclinic, P1 (#2); a = 10.971(2) {\AA}, b = 12.134(2) {\AA}, c = 15.280(4) {\AA}. α = 89.94(2)°, β = 110.00(2)°, γ = 116.75(2)°, Z=2] were characterized by single-crystal X-ray diffraction. Both analyses reveal monomeric structures with the β-ketoiminate ligands coordinated to the Ba2+ center through all available oxygen and nitrogen atoms. These complexes are substantially more volatile than Ba(2,2,6,6,-tetramethyl-3,5-heptanedionate)2 but less so than the most volatile Ba(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)2·polyether complexes.",
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TY - JOUR

T1 - Approaches to Alkaline Earth Metal-Organic Chemical Vapor Deposition Precursors. Synthesis and Characterization of Barium Fluoro-β-ketoiminate Complexes Having Appended Polyether "Lariats"

AU - Neumayer, Deborah A.

AU - Belot, John A.

AU - Feezel, Richard L.

AU - Reedy, Charles

AU - Stern, Charlotte L.

AU - Marks, Tobin J

AU - Liable-Sands, Louise M.

AU - Rheingold, Arnold L.

PY - 1998

Y1 - 1998

N2 - The synthesis and characterization of a family of β-ketoimines derived from 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hfa) and the corresponding volatile barium β-keioiminate - polyether complexes having the general formula Ba[CF3COCHC(NR)CF3]2 where R = (CH2CH2O)2CH3, (CH2CH2O)2CH2CH3, and (CH2CH2O)3CH2CH3 is reported. These complexes can be transported in the vapor phase at 160 °C/0.05 Torr without decomposition. The β-ketoiminate ligands are synthesized by condensation of the appropriate amine-terminated poly(ethylene oxide)s with the trimethylsilyl enol ether derivative of hfa and converted to barium β-ketoiminate - polyether complexes by reaction with BaH2. The poly(ethylene oxide) amines are in turn synthesized by triphenylphosphine-mediated reduction of the corresponding poly(ethylene oxide) azides (synthesized via the tosylates) to afford the amines in good yields and analytical purity. The amines, β-ketoimines, and barium complexes were characterized by elemental analysis, 1H, 19F, and 13C NMR spectroscopy, mass spectroscopy, and thermogravimetric analysis. The eight-and ten-coordinate Ba2+ complexes having the formula Ba[CF3COCHC(NR)CF3]2 where R = (CH2CH2O)2CH2CH3 [C22H28N2F12O6Ba; space group = monoclinic, P21; a = 12.1175(2) Å, b = 14.9238(2) Å, c = 16.9767(3) Å, a = γ = 90°, β = 90.0840(10)°, Z = 4] and R = (CH2CH2O)3CH2CH3 [C26H36N2F12O8Ba; space group = triclinic, P1 (#2); a = 10.971(2) Å, b = 12.134(2) Å, c = 15.280(4) Å. α = 89.94(2)°, β = 110.00(2)°, γ = 116.75(2)°, Z=2] were characterized by single-crystal X-ray diffraction. Both analyses reveal monomeric structures with the β-ketoiminate ligands coordinated to the Ba2+ center through all available oxygen and nitrogen atoms. These complexes are substantially more volatile than Ba(2,2,6,6,-tetramethyl-3,5-heptanedionate)2 but less so than the most volatile Ba(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)2·polyether complexes.

AB - The synthesis and characterization of a family of β-ketoimines derived from 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hfa) and the corresponding volatile barium β-keioiminate - polyether complexes having the general formula Ba[CF3COCHC(NR)CF3]2 where R = (CH2CH2O)2CH3, (CH2CH2O)2CH2CH3, and (CH2CH2O)3CH2CH3 is reported. These complexes can be transported in the vapor phase at 160 °C/0.05 Torr without decomposition. The β-ketoiminate ligands are synthesized by condensation of the appropriate amine-terminated poly(ethylene oxide)s with the trimethylsilyl enol ether derivative of hfa and converted to barium β-ketoiminate - polyether complexes by reaction with BaH2. The poly(ethylene oxide) amines are in turn synthesized by triphenylphosphine-mediated reduction of the corresponding poly(ethylene oxide) azides (synthesized via the tosylates) to afford the amines in good yields and analytical purity. The amines, β-ketoimines, and barium complexes were characterized by elemental analysis, 1H, 19F, and 13C NMR spectroscopy, mass spectroscopy, and thermogravimetric analysis. The eight-and ten-coordinate Ba2+ complexes having the formula Ba[CF3COCHC(NR)CF3]2 where R = (CH2CH2O)2CH2CH3 [C22H28N2F12O6Ba; space group = monoclinic, P21; a = 12.1175(2) Å, b = 14.9238(2) Å, c = 16.9767(3) Å, a = γ = 90°, β = 90.0840(10)°, Z = 4] and R = (CH2CH2O)3CH2CH3 [C26H36N2F12O8Ba; space group = triclinic, P1 (#2); a = 10.971(2) Å, b = 12.134(2) Å, c = 15.280(4) Å. α = 89.94(2)°, β = 110.00(2)°, γ = 116.75(2)°, Z=2] were characterized by single-crystal X-ray diffraction. Both analyses reveal monomeric structures with the β-ketoiminate ligands coordinated to the Ba2+ center through all available oxygen and nitrogen atoms. These complexes are substantially more volatile than Ba(2,2,6,6,-tetramethyl-3,5-heptanedionate)2 but less so than the most volatile Ba(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)2·polyether complexes.

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