| 178325-36-5

• CAS: 178325-36-5
• 化学式: C₂₂H₅₂Cl₂NOP₂ScSi₂
• 分子量: 580.641
• InChiKey: GBCWVQUGGVTJFT-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  、 trimethylsilylmethyllithium 以 甲苯 为溶剂， 以72%的产率得到bis[di(propan-2-yl)phosphanylmethyl-dimethylsilyl]azanide;methanidyl(trimethyl)silane;scandium(3+)
  参考文献：
  名称：

  五配位Scan二烷基配合物ScR 2 [N（SiMe 2 CH 2 PPr i 2）2 ]（R = Me，Et，CH 2 SiMe 3）的合成与表征

  摘要：

  报道了含有两个烃基的新的phosph膦配合物的制备。因此，酰胺二膦配体前体LiN（SiMe 2 CH 2 PPr i 2）2与ScCl 3（THF）3在甲苯中于100°C的反应导致形成ScCl 2（THF）[N（SiMe 2 CH 2） PPr i 2）2可以通过泵入固态除去THF分子。该分子的X射线晶体结构表明它是具有扭曲的八面体几何形状的单体，该八面体几何结构具有易位的氯化物配体和经子午线结合的三齿配体。溶液的NMR光谱也与此几何形状一致。烷基锂试剂RLi（其中R = Me，Et和CH 2 SiMe 3）的加入导致形成式ScR 2 [N（SiMe 2 CH 2 PPr i 2）2 ]的双（烃基）衍生物。这些是已表征的第一批二烷基取代的scan络合物。ScEt 2的固态X射线结构[N（SiMe 2 CH 2 PPr i 2）2 ]和Sc（CH 2 SiMe 3）2 [N（SiMe 2 CH

  DOI：

  10.1021/om960052q
• 作为产物：
  描述：

  LiN(SiMe2CH2PPr(i)2)2 、 [scandium(III)(chloride)3(tetrahydrofuran)3] 以 甲苯 为溶剂， 以83%的产率得到
  参考文献：
  名称：

  五配位Scan二烷基配合物ScR 2 [N（SiMe 2 CH 2 PPr i 2）2 ]（R = Me，Et，CH 2 SiMe 3）的合成与表征

  摘要：

  报道了含有两个烃基的新的phosph膦配合物的制备。因此，酰胺二膦配体前体LiN（SiMe 2 CH 2 PPr i 2）2与ScCl 3（THF）3在甲苯中于100°C的反应导致形成ScCl 2（THF）[N（SiMe 2 CH 2） PPr i 2）2可以通过泵入固态除去THF分子。该分子的X射线晶体结构表明它是具有扭曲的八面体几何形状的单体，该八面体几何结构具有易位的氯化物配体和经子午线结合的三齿配体。溶液的NMR光谱也与此几何形状一致。烷基锂试剂RLi（其中R = Me，Et和CH 2 SiMe 3）的加入导致形成式ScR 2 [N（SiMe 2 CH 2 PPr i 2）2 ]的双（烃基）衍生物。这些是已表征的第一批二烷基取代的scan络合物。ScEt 2的固态X射线结构[N（SiMe 2 CH 2 PPr i 2）2 ]和Sc（CH 2 SiMe 3）2 [N（SiMe 2 CH

  DOI：

  10.1021/om960052q

文献信息

• Synthesis, characterization, and reactivity of scandium chloro, alkyl, aryl, and borohydride comple×es, Sc(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)R[N(SiMe<sub>2</sub>CH<sub>2</sub>P<sup>i</sup>Pr<sub>2</sub>)<sub>2</sub>] (R = Cl, Me, Ph, and BH<sub>4</sub>)
  作者：Michael D. Fryzuk、Garth R. Giesbrecht、Steven J. Rettig

  DOI：10.1139/cjc-78-7-1003

  日期：——

  Reaction of ScCl2(THF)[N((SiMe2CH2PPr2)-Pr-i)(2)] with NaCp(DME) leads to Sc(eta(5)-C5H5)Cl[N((SiMe2CH2PPr2)-Pr-i)(2)] (1). The X-ray crystal structure shows the scandium centre to reside in a square pyramidal environment with the [N((SiMe2CH2PPr2)-Pr-i)(2)] - ligand bound in a pseudo-meridional fashion. The H-1 NMR spectrum is consistent with a C-s symmetric structure in solution. Metathesis of the chloride ligand with RLi (R = Me, Ph, BH4) yields the five-coordinate species Sc(eta(5)-C5H5)R[N((SiMe2CH2PPr2)-Pr-i)(2)]. Phenyl 3 and borohydride 4 are isolated as crystalline solids, while methyl 2 resisted crystallization. 2-4 exhibit H-1 NMR spectra consistent with C-s symmetric solution structures. Sc(eta(5)-C5H5)Ph[N((SiMe2CH2PPr2)-Pr-i)(2)] (3) was characterized in the solid state and found to have a similar geometry to that of the parent chloride. Reaction of Sc(eta(5)-C5H5)Me[N((SiMe2CH2PPr2)-Pr-i)(2)] (2) with NH2R (R = Ph, Bu-t) yields the amides Sc(eta(5)-C5H5)NHPh[N((SiMe2CH2PPr2)-Pr-i)(2)] (5) and Sc(eta(5)-C5H5)(NHBu)-Bu-t- [N((SiMe2CH2PPr2)-Pr-i)(2)] (6) via sigma-bond metathesis routes; these reactions are accompanied by a competing reaction at the scandium-amide bond to produce the protonated ligand, HN((SiMe2CH2PPr2)-Pr-i)(2) 5 and 6 are also produced by salt-elimination from the chloride 1 and LiNHR (R = Ph, Bu-t). Sc(eta(5)-C5H5)(BH4)[N((SiMe2CH2PPr2)-Pr-i)(2)] (4) reacts with PMe3 to produce the putative hydride, Sc(eta(5)-C5H5)H[N((SiMe2CH2PPr2)-Pr-i)(2)] (7); this species was identified in solution. An equilibrium between 4, PMe3, 7, and PMe3,BH3 exists which greatly favors the starting scandium-borohydride. Crystals of Sc(eta(5)-C5H5)Cl[N((SiMe2CH2PPr2)-Pr-i)(2)] (1) are monoclinic, a = 17.409(2), b = 10.0803(7), c = 17.688(2) A, beta = 94.606(8) degrees, Z = 4, space group P2(1)/c; and those of Sc(eta(5)-C5H5)Ph[N((SiMe2CH2PPr2)-Pr-i)(2)] (3) are triclinic, a = 10.5129(15), b = 19.124(2), c = 9.114(2) A, alpha = 95.582(13), beta = 107.047(12), gamma = 90.042(11)degrees, Z = 2, space group P. The structures were solved by Patterson (1) and direct (3) methods and refined by full-matrix least-squares procedures to R = 0.047 and 0.054 (R-w = 0.042 and 0.049) for 2414 and 2844 reflections with I greater than or equal to 3 sigma(I), respectively.