(μ-1,3-propanedithiolato)[Fe(CO)3][Fe(CO)2(1,3,5-triaza-7-phosphaadamantane)] | 777076-59-2

• 英文名称: (μ-1,3-propanedithiolato)[Fe(CO)3][Fe(CO)2(1,3,5-triaza-7-phosphaadamantane)]
• 英文别名: (μ-SCH2CH2CH2S)[Fe(CO)2(1,3,5-triaza-7-phosphaadamantane)][Fe(CO)3]；(μ-pdt)[Fe(CO)3][Fe(CO)2(PTA)]
• CAS: 777076-59-2
• 化学式: C₁₄H₁₈Fe₂N₃O₅PS₂
• 分子量: 515.114
• InChiKey: AYNAVMUUIJXZPM-UHFFFAOYSA-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：

  乙醇 、 (μ-1,3-propanedithiolato)[Fe(CO)3][Fe(CO)2(1,3,5-triaza-7-phosphaadamantane)] 、 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane 以 乙腈 为溶剂， 以44%的产率得到(μ-pdt)[Fe(CO)2(DAPTA)][Fe(CO)2(PTA)]*C2H5OH
  参考文献：
  名称：

  An approach to water-soluble hydrogenase active site models: Synthesis and electrochemistry of diiron dithiolate complexes with 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane ligand(s)

  摘要：

  In order to improve the hydro- and protophilicity of the active site models of the Fe-only hydrogenases, three diiron dithiolate complexes with DAPTA ligand(s) (DAPTA=3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonanc), (mu-pdt)[Fe(CO)(2)][Fe(CO)(2)(DAPTA)] (1, pdt = 1,3-propanedithiolato), (mu-pdt)[Fe(CO)(2)(DAPTA)](2) (2) and (mu-pdt)[Fe(CO)(2)(PTA)][Fe(CO)(2)(DAPTA)] (3), were prepared and spectroscopically characterized. The water solubility of DAPTA-coordinate complexes 1-3 is better than that of the PTA-coordinate analogues. With complexes 1-3 as electrocatalysts, the overvoltage is reduced by 460-770 mV for proton reduction from acetic acid at low concentration in CH3CN. Significant decrease, up to 420 mV, in reduction potential for the Fe(I)Fe(I) to Fe(I)Fe(0) process and the curve-crossing phenomenon are observed in cyclic voltammograms of 2 and 3 in CH3CN/H2O mixtures. The introduction of the DAPTA ligand to the diiron dithiolate model complexes indeed makes the water solubility of 2 and 3 sufficient for electrochemical studies in pure water, which show that the proton reduction from acetic acid in pure water is electrochemically catalyzed by 2 and 3 at ca. -1.3 V vs. NHE. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.08.082
• 作为产物：
  描述：

  1,3-(μ-propanedithiolato)diironhexacarbonyl 、 1,3,5-三氮杂-7-磷杂金刚烷 生成 (μ-1,3-propanedithiolato)[Fe(CO)3][Fe(CO)2(1,3,5-triaza-7-phosphaadamantane)]
  参考文献：
  名称：

  An approach to water-soluble hydrogenase active site models: Synthesis and electrochemistry of diiron dithiolate complexes with 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane ligand(s)

  摘要：

  In order to improve the hydro- and protophilicity of the active site models of the Fe-only hydrogenases, three diiron dithiolate complexes with DAPTA ligand(s) (DAPTA=3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonanc), (mu-pdt)[Fe(CO)(2)][Fe(CO)(2)(DAPTA)] (1, pdt = 1,3-propanedithiolato), (mu-pdt)[Fe(CO)(2)(DAPTA)](2) (2) and (mu-pdt)[Fe(CO)(2)(PTA)][Fe(CO)(2)(DAPTA)] (3), were prepared and spectroscopically characterized. The water solubility of DAPTA-coordinate complexes 1-3 is better than that of the PTA-coordinate analogues. With complexes 1-3 as electrocatalysts, the overvoltage is reduced by 460-770 mV for proton reduction from acetic acid at low concentration in CH3CN. Significant decrease, up to 420 mV, in reduction potential for the Fe(I)Fe(I) to Fe(I)Fe(0) process and the curve-crossing phenomenon are observed in cyclic voltammograms of 2 and 3 in CH3CN/H2O mixtures. The introduction of the DAPTA ligand to the diiron dithiolate model complexes indeed makes the water solubility of 2 and 3 sufficient for electrochemical studies in pure water, which show that the proton reduction from acetic acid in pure water is electrochemically catalyzed by 2 and 3 at ca. -1.3 V vs. NHE. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.08.082

文献信息

• The Hydrophilic Phosphatriazaadamantane Ligand in the Development of H₂ Production Electrocatalysts:  Iron Hydrogenase Model Complexes
  作者：Rosario Mejia-Rodriguez、Daesung Chong、Joseph H. Reibenspies、Manuel P. Soriaga、Marcetta Y. Darensbourg

  DOI：10.1021/ja039394v

  日期：2004.9.1

  both cases the parent complex is reclaimed during one cycle under the electrochemical conditions and H(2) production catalysis develops from the neutral species. The order of proton/electron addition to the catalyst, i.e., the electrochemical mechanism, is dependent on the extent of P-donor ligand substitution and on the acid strength. Cyclic voltammetric curve-crossing phenomena was observed and analyzed

  作为 [Fe]H(2)ase 中双核活性位点产氢能力的功能仿生学，Fe(I)Fe(I) 有机金属配合物，(mu-pdt)[Fe(CO)(2)PTA ](2), 1-PTA(2), (pdt = SCH(2)CH(2)CH(2)S; PTA = 1,3,5-triaza-7-phosphaadamantane), 和 (mu-pdt) [Fe(CO)(3)][Fe(CO)(2)PTA]，1-PTA，已合成并充分表征。为了与疏水性 (mu-pdt)[Fe(CO)(2)(PMe(3))](2) 和 [(mu-H)(mu-pdt)[Fe(CO)(2)(PMe (3))](2)](+) 类似物，1-PTA(2) 和 1-(PTA.H(+))(2) 的电化学响应在乙腈和乙腈/水混合物中没有记录和醋酸的存在。H(2) 的产生和电流对酸浓度的依赖性表明复合物是溶液电催化剂，可将 H(+) 从 CH(3)CN