| 1050381-21-9

• CAS: 1050381-21-9
• 化学式: C₂₄H₂₀B*C₅₆H₅₇NP₃S₂U
• 分子量: 1458.39
• InChiKey: WGTJGMFYZDXBFS-QHHCSYJCSA-N

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：

  、 三苯基氧化膦 以 氘代四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Organouranium Complexes with Phosphinine-Based SPS Pincer Ligands. Variations with the Substituent at the Phosphorus Atom

  摘要：

  Reaction of [K(Et(2)O)][SPS(Me)] with [U(Cp*)(BH(4))(3)] or [U(COT)(BH(4))(2)(THF)] in THF gave the expected substitution products [U(Cp*)(BH(4))(2)(SPS(Me))] (1) and [U(COT)(BH(4))(SPS(Me))] (2), respectively. Protonolysis of 2 with [NEt(3)H][BPh(4)] afforded the cationic complex [U(COT)(SPS(Me))(NEt(3))][BPh(4)] (3), which was transformed into [U(COT)(SPS(Me))(L)][BPh(4)] [L = OPPh(3) (4) or HMPA (5)]. Changing [K(Et(2)O)][SPS(Me)] with [Na][SPS(OMe)] in its reaction with [U(COT)(BH(4))(2)(THF)] afforded a mixture of complexes, among which [U(COT)(BH(4))(SPS(H))] (6) was deposited as red crystals of a THF solvate. Complex 6 was isolated in 79% yield from the reaction of [U(COT)(BH(4))(2)(THF)] and SPS in the presence of a catalytic amount of NaBH(4); the key intermediate of the reaction is [Na(THF)(x)][SPS(H) center dot BH(3)], formed by addition of NaBH4 to SPS, which reacts with [U(COT)(BH(4))(2)(THF)] to give 6 and NaBH(4). The X-ray crystal structures of 1 . 4.5C(6)H(12), 2 . THF, 5 . Et(2)O, and 6 . 1.5THF indicate that the central moiety of the SPS ligand can be considered as a classical phosphine, the anionic charge being stabilized by delocalization over the five carbon atoms of the phosphahexadienyl anion and negative hyperconjugation into the two Ph(2)PS pendant arms. The X-ray crystal structures of [{U(COT)(S(2)PPh(2))(mu-OMe)}(2)] and [{U(COT)}(4){U(THF)(3)}(2)(mu(3)-S)(8)], which resulted from decomposition of the SPS ligand, are also presented.

  DOI：

  10.1021/om8003493
• 作为产物：
  描述：

  、 triethylammonium tetraphenylborate 以 四氢呋喃 为溶剂， 以94%的产率得到
  参考文献：
  名称：

  Organouranium Complexes with Phosphinine-Based SPS Pincer Ligands. Variations with the Substituent at the Phosphorus Atom

  摘要：

  Reaction of [K(Et(2)O)][SPS(Me)] with [U(Cp*)(BH(4))(3)] or [U(COT)(BH(4))(2)(THF)] in THF gave the expected substitution products [U(Cp*)(BH(4))(2)(SPS(Me))] (1) and [U(COT)(BH(4))(SPS(Me))] (2), respectively. Protonolysis of 2 with [NEt(3)H][BPh(4)] afforded the cationic complex [U(COT)(SPS(Me))(NEt(3))][BPh(4)] (3), which was transformed into [U(COT)(SPS(Me))(L)][BPh(4)] [L = OPPh(3) (4) or HMPA (5)]. Changing [K(Et(2)O)][SPS(Me)] with [Na][SPS(OMe)] in its reaction with [U(COT)(BH(4))(2)(THF)] afforded a mixture of complexes, among which [U(COT)(BH(4))(SPS(H))] (6) was deposited as red crystals of a THF solvate. Complex 6 was isolated in 79% yield from the reaction of [U(COT)(BH(4))(2)(THF)] and SPS in the presence of a catalytic amount of NaBH(4); the key intermediate of the reaction is [Na(THF)(x)][SPS(H) center dot BH(3)], formed by addition of NaBH4 to SPS, which reacts with [U(COT)(BH(4))(2)(THF)] to give 6 and NaBH(4). The X-ray crystal structures of 1 . 4.5C(6)H(12), 2 . THF, 5 . Et(2)O, and 6 . 1.5THF indicate that the central moiety of the SPS ligand can be considered as a classical phosphine, the anionic charge being stabilized by delocalization over the five carbon atoms of the phosphahexadienyl anion and negative hyperconjugation into the two Ph(2)PS pendant arms. The X-ray crystal structures of [{U(COT)(S(2)PPh(2))(mu-OMe)}(2)] and [{U(COT)}(4){U(THF)(3)}(2)(mu(3)-S)(8)], which resulted from decomposition of the SPS ligand, are also presented.

  DOI：

  10.1021/om8003493