Neumayer Deborah A., Belot John A., Feezel Richard L., Reedy Charles, Stern Charlotte L., Marks Tobin J., Liable-Sands Louise M., Rheingold Arnold L.
Department of Chemistry, University of Delaware, Newark, Delaware 19716.
Inorg Chem. 1998 Oct 19;37(21):5625-5633. doi: 10.1021/ic980208+.
The synthesis and characterization of a family of beta-ketoimines derived from 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hfa) and the corresponding volatile barium beta-ketoiminate-polyether complexes having the general formula BaCF(3)COCHC(NR)CF(3) where R = (CH(2)CH(2)O)(2)CH(3), (CH(2)CH(2)O)(2)CH(2)CH(3), and (CH(2)CH(2)O)(3)CH(2)CH(3) is reported. These complexes can be transported in the vapor phase at 160 degrees C/0.05 Torr without decomposition. The beta-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 beta-ketoiminate-polyether complexes by reaction with BaH(2). 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, beta-ketoimines, and barium complexes were characterized by elemental analysis, (1)H, (19)F, and (13)C NMR spectroscopy, mass spectroscopy, and thermogravimetric analysis. The eight- and ten-coordinate Ba(2+) complexes having the formula BaCF(3)COCHC(NR)CF(3) where R = (CH(2)CH(2)O)(2)CH(2)CH(3) [C(22)H(28)N(2)F(12)O(6)Ba; space group = monoclinic, P2(1); a = 12.1175(2) Å, b = 14.9238(2) Å, c = 16.9767(3) Å, alpha = gamma = 90 degrees, beta = 90.0840(10) degrees, Z = 4] and R = (CH(2)CH(2)O)(3)CH(2)CH(3) [C(26)H(36)N(2)F(12)O(8)Ba; space group = triclinic, P&onemacr; (#2); a = 10.971(2) Å, b = 12.134(2) Å, c = 15.280(4) Å, alpha = 89.94(2) degrees, beta = 110.00(2) degrees, gamma = 116.75(2) degrees, Z = 2] were characterized by single-crystal X-ray diffraction. Both analyses reveal monomeric structures with the beta-ketoiminate ligands coordinated to the Ba(2+) 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.
报道了一系列由1,1,1,5,5,5-六氟-2,4-戊二酮（hfa）衍生的β-酮亚胺的合成与表征，以及通式为BaCF(3)COCHC(NR)CF(3)（其中R = (CH(2)CH(2)O)(2)CH(3)、(CH(2)CH(2)O)(2)CH(2)CH(3)和(CH(2)CH(2)O)(3)CH(2)CH(3)）的相应挥发性钡β-酮亚胺-聚醚配合物。这些配合物可在160℃/0.05托的气相中传输而不分解。β-酮亚胺配体通过适当的胺基封端的聚环氧乙烷与hfa的三甲基硅基烯醇醚衍生物缩合合成，并通过与BaH(2)反应转化为钡β-酮亚胺-聚醚配合物。聚环氧乙烷胺则通过三苯基膦介导还原相应的聚环氧乙烷叠氮化物（通过对甲苯磺酸酯合成）来合成，以高收率和分析纯得到胺。通过元素分析、(1)H、(19)F和(13)C核磁共振光谱、质谱和热重分析对胺、β-酮亚胺和钡配合物进行了表征。通过单晶X射线衍射对通式为BaCF(3)COCHC(NR)CF(3)（其中R = (CH(2)CH(2)O)(2)CH(2)CH(3) [C(22)H(28)N(2)F(12)O(6)Ba；空间群 = 单斜晶系，P2(1)；a = 12.1175(2) Å，b = 14.9238(2) Å，c = 16.9767(3) Å，α = γ = 90°，β = 90.0840(10)°，Z = 4]）和R = (CH(2)CH(2)O)(3)CH(2)CH(3) [C(26)H(36)N(2)F(12)O(8)Ba；空间群 = 三斜晶系，P&onemacr; (#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]）的八配位和十配位Ba(2+)配合物进行了表征。两种分析均揭示了单体结构，其中β-酮亚胺配体通过所有可用的氧和氮原子与Ba(2+)中心配位。这些配合物的挥发性比Ba(2,2,6,6-四甲基-3,5-庚二酮)(2)大得多，但比挥发性最高的Ba(1,1,1,5,5,5-六氟-2,4-戊二酮)(2).聚醚配合物小。
