| 1186508-22-4

• 分子结构分类: 有机化合物 - 有机杂环化合物
• CAS: 1186508-22-4
• 化学式: C₅₇H₄₇N₂RhSi₂
• 分子量: 919.09
• InChiKey: IBZBCNXFHKODHU-UHFFFAOYSA-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：

  、 三苯基膦 以 苯 为溶剂， 以73%的产率得到
  参考文献：
  名称：

  High Oxidation State Rhodium and Iridium Bis(silyl)dihydride Complexes Supported by a Chelating Pyridyl-Pyrrolide Ligand

  摘要：

  New rhodium and iridium complexes containing the bidentate ligand 3,5-diphenyl-2-(2-pyridyl)pyrrolide (PyPyr) were prepared. The bis(ethylene) complex (PyPyr)Rh(C2H4)(2) (3) reacted with HSiEt3, HSiPh3, and (HSiBuPh2)-Bu-t to produce the 16-electron Rh(V) bis(silyl)dihydrides (PyPyr)Rh(H)(2)(SiEt3)(2) (8), (PyPyr)Rh(H)(2)(SiPh3)(2) (9), and (PyPyr)Rh(H)(2)((SiBuPh2)-Bu-t)(2) (10), respectively. The analogous Ir(V) bis(silyl)dihyride (PyPyr)Ir(H)(2)(SiPh3)(2) (11) has also been synthesized. X-ray crystallography reveals that 9-11 adopt a coordination geometry best described as a bicapped tetrahedron. Silane elimination from 9 and 10 occurred in the presence of either HSiEt3 or PPh3. Mechanistic studies of the silane exchange process involving 10 and free HSiEt3 (to give 8) indicate that this process occurs by rate-limiting reductive elimination of (HSiBuPh2)-Bu-t from 10 to generate a 14-electron Rh(III) intermediate of the type (PyPyr)Rh(H)((SiBuPh2)-Bu-t).

  DOI：

  10.1021/ja9035169
• 作为产物：
  描述：

  叔丁基二苯基硅烷 以 氘代苯 、 苯 为溶剂， 生成
  参考文献：
  名称：

  High Oxidation State Rhodium and Iridium Bis(silyl)dihydride Complexes Supported by a Chelating Pyridyl-Pyrrolide Ligand

  摘要：

  New rhodium and iridium complexes containing the bidentate ligand 3,5-diphenyl-2-(2-pyridyl)pyrrolide (PyPyr) were prepared. The bis(ethylene) complex (PyPyr)Rh(C2H4)(2) (3) reacted with HSiEt3, HSiPh3, and (HSiBuPh2)-Bu-t to produce the 16-electron Rh(V) bis(silyl)dihydrides (PyPyr)Rh(H)(2)(SiEt3)(2) (8), (PyPyr)Rh(H)(2)(SiPh3)(2) (9), and (PyPyr)Rh(H)(2)((SiBuPh2)-Bu-t)(2) (10), respectively. The analogous Ir(V) bis(silyl)dihyride (PyPyr)Ir(H)(2)(SiPh3)(2) (11) has also been synthesized. X-ray crystallography reveals that 9-11 adopt a coordination geometry best described as a bicapped tetrahedron. Silane elimination from 9 and 10 occurred in the presence of either HSiEt3 or PPh3. Mechanistic studies of the silane exchange process involving 10 and free HSiEt3 (to give 8) indicate that this process occurs by rate-limiting reductive elimination of (HSiBuPh2)-Bu-t from 10 to generate a 14-electron Rh(III) intermediate of the type (PyPyr)Rh(H)((SiBuPh2)-Bu-t).

  DOI：

  10.1021/ja9035169