| 1343439-80-4

• CAS: 1343439-80-4；1344995-02-3
• 化学式: C₁₅H₂₂CoN₃O₄S₂Si
• 分子量: 459.568
• InChiKey: ZFAMUPVEFGQTKO-IRYVOTIRSA-M

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：

  以 苯 为溶剂， 以1%的产率得到(η(5)-C5H5)Co(S2C2(COOMe)2)(CHSiMe3)
  参考文献：
  名称：

  Syntheses and reactivities of azido coordinated CpCo(dithiolene) complexes

  摘要：

  Azido coordinated dithiolene complexes [CpCo(N-3)(S2C2(CO2Me)(2)}(S-(CHRR2)-R-1)], where R-1, R-2 = H (4a); R-1 = H, R-2 = SiMe3 (4b); R-1 = H, R-2 = CO2Et (4c), were synthesized by the reactions of the corresponding Cl- coordinated precursors [CpCo(Cl)(S2C2(CO2Me)(2))(S-(CHRR2)-R-1)] (3a-3c) with sodium azide. The Cl- coordinated complex 3d (R-1, R-2 = CO2Me) did not produce any N-3(-) coordinated complexes but formed the (CRR2)-R-1-bridged alkylidene adduct [CpCo{S2C2(CO2Me)(2))((CRR2)-R-1)] (2d; R-1, R-2= CO2Me). The structure of 4a was determined by X-ray diffraction study. In the molecular structure of 4a, the coordinated N-3(-) ligand and (CHRR2)-R-1 group were located at the same side with respect to the dithiolene ring (syn form), although the corresponding Cl- precursor (3a; R-1, R-2 = H) was anti form. A structural conversion of syn/anti was conceivable during the Cl-/N-3(-) ligand exchange. Thermal (80 degrees C) and photochemical reactions (Hg lamp) of 4a-4c were performed. Among them, 4c was relatively well reacted compared with the others to form the (CRR2)-R-1-bridged alkylidene adduct (2c; R-1 = H, R-2 = CO2Et), followed by a formal HN3 elimination, and the reaction also produced non-adduct of the cobalt dithiolene complex [CpCo{S2C2(CO2Me)(2))] (1). The electrochemical 1e(-) reduction of 4c underwent a formal N-3(-) ligand elimination, and successive second reduction caused the (CHRR2)-R-1 group elimination or reformed the (CRR2)-R-1-bridged alkylidene adduct 2c. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2011.08.023
• 作为产物：
  描述：

  (η(5)-C5H5)Co(Cl)(S2C2(COOMe)2)(CH2SiMe3) 、 sodium azide 以 二氯甲烷 、 水 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Syntheses and reactivities of azido coordinated CpCo(dithiolene) complexes

  摘要：

  Azido coordinated dithiolene complexes [CpCo(N-3)(S2C2(CO2Me)(2)}(S-(CHRR2)-R-1)], where R-1, R-2 = H (4a); R-1 = H, R-2 = SiMe3 (4b); R-1 = H, R-2 = CO2Et (4c), were synthesized by the reactions of the corresponding Cl- coordinated precursors [CpCo(Cl)(S2C2(CO2Me)(2))(S-(CHRR2)-R-1)] (3a-3c) with sodium azide. The Cl- coordinated complex 3d (R-1, R-2 = CO2Me) did not produce any N-3(-) coordinated complexes but formed the (CRR2)-R-1-bridged alkylidene adduct [CpCo{S2C2(CO2Me)(2))((CRR2)-R-1)] (2d; R-1, R-2= CO2Me). The structure of 4a was determined by X-ray diffraction study. In the molecular structure of 4a, the coordinated N-3(-) ligand and (CHRR2)-R-1 group were located at the same side with respect to the dithiolene ring (syn form), although the corresponding Cl- precursor (3a; R-1, R-2 = H) was anti form. A structural conversion of syn/anti was conceivable during the Cl-/N-3(-) ligand exchange. Thermal (80 degrees C) and photochemical reactions (Hg lamp) of 4a-4c were performed. Among them, 4c was relatively well reacted compared with the others to form the (CRR2)-R-1-bridged alkylidene adduct (2c; R-1 = H, R-2 = CO2Et), followed by a formal HN3 elimination, and the reaction also produced non-adduct of the cobalt dithiolene complex [CpCo{S2C2(CO2Me)(2))] (1). The electrochemical 1e(-) reduction of 4c underwent a formal N-3(-) ligand elimination, and successive second reduction caused the (CHRR2)-R-1 group elimination or reformed the (CRR2)-R-1-bridged alkylidene adduct 2c. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2011.08.023