bis[ditert-butylphosphanylmethyl(dimethyl)silyl]azanide;cobalt(2+);trifluoromethanesulfonate | 960079-54-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: bis[ditert-butylphosphanylmethyl(dimethyl)silyl]azanide;cobalt(2+);trifluoromethanesulfonate
• CAS: 960079-54-3
• 化学式: C₂₃H₅₂CoF₃NO₃P₂SSi₂
• 分子量: 656.844
• InChiKey: WHYAJMXFHIFCFI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  9.06
• 重原子数：
  36
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  66.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  [((t)Bu2PCH2SiMe2)2N]CoCl 、 三氟甲磺酸三甲基硅酯 以 苯 为溶剂， 生成 bis[ditert-butylphosphanylmethyl(dimethyl)silyl]azanide;cobalt(2+);trifluoromethanesulfonate
  参考文献：
  名称：

  Exploring the Reactivity of Four-Coordinate PNPCoX with Access to Three-Coordinate Spin Triplet PNPCo

  摘要：

  The compounds (PNP)CoX, where PNP is ((Bu2PCH2SiMe2)-Bu-t)(2)N- and X is Cl, l, N-3, OAr, OSO2CF3 and N(H)Ar, are reported. Some of these show magnetic susceptibility, color, and H-1 NMR evidence of being in equilibrium between a blue, tetrahedral S = 3/2 state and a red, planar S = 1/2 state; the equilibrium populations are influenced by subtle solvent effects (e.g., benzene and cyclohexane are different), as well as by temperature. Attempted oxidation to Co(III) with O-2 occurs instead at phosphorus, giving [P(O)NP(O)]CoX species. The single O-atom transfer reagent Phl=O likewise oxidizes P. Even l(2) oxidizes P to give the pendant phosphonium species ((t)Bu2P(l)CH2SiMe2-(NSiMe2CH2PBU2)-B-t)Col(2) with a tetrahedral S = 3/2 cobalt; the solid-state structure shows intermolecular Pl center dot center dot center dot lCo interactions. Attempted alkyl metathesis of PNPCoX inevitably results in reduction, forming PNPCo, which is a spin triplet with planar T-shaped coordination geometry with no agostic interaction. Triplet PNPCo binds N-2(weakly) and CO (whose low CO stretching frequency indicates strong PNP -> Co donor power), but not ethene or MeCCMe.

  DOI：

  10.1021/ic701171p