Fe2[(SCHMe)2NH](CO)4(PMe3)2 | 1005458-39-8

• 英文名称: Fe2[(SCHMe)2NH](CO)4(PMe3)2
• CAS: 1005458-39-8
• 化学式: C₁₄H₂₇Fe₂NO₄P₂S₂
• 分子量: 511.146
• InChiKey: RXBAIMITGPHIPT-RFKUEUTRSA-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：

  Fe2[(SCHMe)2NH](CO)4(PMe3)2 、 对甲苯磺酸 以 氘代乙腈 为溶剂， 生成 [Fe2((SCHMe)2NH)(μ-H)(CO)4(PMe3)2](1+)
  参考文献：
  名称：

  Desymmetrized Diiron Azadithiolato Carbonyls: A Step Toward Modeling the Iron-Only Hydrogenases

  摘要：

  Condensation of Fe-2(SH)(2)(CO)(6), acetaldehyde, and (NH4)(2)CO3 affords the methyl-substituted azadithiolate Fe-2[(SCHMe)(2)NH](CO)(6) (1). The complex exists mainly (similar to 95%) as the meso diastercomer, but the d,l diastereoisomers could be detected. DFT calculations predict that the meso isomer would be 2.5 kcal/mol more stable than the d, 1 isomer due to conventional nonbonding interactions between the methyl groups and the ring hydrogen atoms. Crystallographic analysis of meso-1 confirms that the two methyl groups are equatorial, constraining the diferraazadithiolate bicycle to a conformation that desymmetrizes the diiron center. The lowered symmetry is confirmed by the observation of two C-13 NMR signals in the FeCO region under conditions of fast turnstile rotation at the Fe(CO)(3) groups. The p& value of the amine in 1 is 7.89 (all pK(a)'s determined in MeCN solution), which is similar to a redetermined value for Fe-2[(SCH2)(2)NH](CO)(6) (2, pK(a) = 7.98) and only slightly less basic than the tertiary amine Fe-2[(SCH2)(2)NMe](CO)(6) (pK(a) = 8.14). Substitution of 1 with PMe3 proceeded via the intermediacy of two isomers of Fe-2[(SCHMe)(2)NH](CO)(5)(PMe3), affording Fe-2[(SCHMe)(2)NH](CO)(4)(PMe3)(2) (3). P-31 NMR spectra confirm that the two PMe3 ligands in 3 are nonequivalent, consistent with the desymmetrizing effect of the dithiolate. The pKa value of the amine in 3 was found to be 11.3. Using triphenylphosphine, we prepared Fe-2[(SCHMe)(2)NH](CO)(5)(PPh3) as a single regioisomer.

  DOI：

  10.1021/om7009599
• 作为产物：
  描述：

  meso-Fe2[(SCHMe)2NH](CO)6 、 三甲基膦 以 氘代乙腈 为溶剂， 生成 Fe2[(SCHMe)2NH](CO)4(PMe3)2
  参考文献：
  名称：

  Desymmetrized Diiron Azadithiolato Carbonyls: A Step Toward Modeling the Iron-Only Hydrogenases

  摘要：

  Condensation of Fe-2(SH)(2)(CO)(6), acetaldehyde, and (NH4)(2)CO3 affords the methyl-substituted azadithiolate Fe-2[(SCHMe)(2)NH](CO)(6) (1). The complex exists mainly (similar to 95%) as the meso diastercomer, but the d,l diastereoisomers could be detected. DFT calculations predict that the meso isomer would be 2.5 kcal/mol more stable than the d, 1 isomer due to conventional nonbonding interactions between the methyl groups and the ring hydrogen atoms. Crystallographic analysis of meso-1 confirms that the two methyl groups are equatorial, constraining the diferraazadithiolate bicycle to a conformation that desymmetrizes the diiron center. The lowered symmetry is confirmed by the observation of two C-13 NMR signals in the FeCO region under conditions of fast turnstile rotation at the Fe(CO)(3) groups. The p& value of the amine in 1 is 7.89 (all pK(a)'s determined in MeCN solution), which is similar to a redetermined value for Fe-2[(SCH2)(2)NH](CO)(6) (2, pK(a) = 7.98) and only slightly less basic than the tertiary amine Fe-2[(SCH2)(2)NMe](CO)(6) (pK(a) = 8.14). Substitution of 1 with PMe3 proceeded via the intermediacy of two isomers of Fe-2[(SCHMe)(2)NH](CO)(5)(PMe3), affording Fe-2[(SCHMe)(2)NH](CO)(4)(PMe3)(2) (3). P-31 NMR spectra confirm that the two PMe3 ligands in 3 are nonequivalent, consistent with the desymmetrizing effect of the dithiolate. The pKa value of the amine in 3 was found to be 11.3. Using triphenylphosphine, we prepared Fe-2[(SCHMe)(2)NH](CO)(5)(PPh3) as a single regioisomer.

  DOI：

  10.1021/om7009599