[Fe2(CO)6(2-(mercaptomethyl)-2-methylpropane-1,3-dithiol(3-))]2[Fe2(CO)6] | 1096537-10-8

• 英文名称: [Fe2(CO)6(2-(mercaptomethyl)-2-methylpropane-1,3-dithiol(3-))]2[Fe2(CO)6]
• CAS: 1096537-10-8
• 化学式: C₂₈H₁₈Fe₆O₁₈S₆
• 分子量: 1169.92
• InChiKey: JMGYBJUCMKSZMV-UHFFFAOYSA-H

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Fe2(CO)6(2-(mercaptomethyl)-2-methylpropane-1,3-dithiol(3-))]2[Fe2(CO)6] 以 二氯甲烷 为溶剂， 生成 [Fe2(CO)5(2-(mercaptomethyl)-2-methylpropane-1,3-dithiol(3-))][Fe2(CO)6L][LFe2(CO)6]
  参考文献：
  名称：

  Synthesis, characterisation of two hexa-iron clusters with {Fe2S2(CO)x} (x=5 or 6) fragments and investigation into their inter-conversion

  摘要：

  Reaction of a trithiol ligand, 2-(mercaptomethyl)-2-methylpropane-1,3-dithiol (H(3)L), with tri-iron dodecacarbonyl in toluene produces two hexa-iron clusters ( 1 and 2). The two clusters are characterised crystallographically and spectroscopically. NMR spectroscopy reveals that the cluster 2 exists in two conformations in equilibrium 2(anti) double left right arrow 2(syn) and the equilibrium constant K(eq) = 0.55 under CO atmosphere. In the cluster 2, the central {Fe(2)S(2)(CO)(6)} sub-unit is flanked by two identical {Fe(2)S(2)(CO)(6)} satellite sub-units through thiolate linkages whereas one of the thiolate linkages can further form Fe-S bond with the proximal Fe atom in one of the two satellite sub-units to produce the cluster 1 by expelling one CO. This conversion can be entirely reversed by continuously purging CO through the solution of the cluster 1. As suggested by DFT calculations, the conversion features a key step, the rotation of the Fe(prox)(CO)(3) to expose a vacant site for exogenic ligand binding ( the S atom from the central sub-unit in this case) with concomitant switch for one of the three CO ligands in the unit of Fe(prox)(CO)(3) from terminal to bridging orientation. The conversion from the clusters 1-2 involving one CO uptake is much faster than its reverse process since the latter is an endergonic process characterised by large reaction barriers, as revealed by the DFT calculations. (C) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.09.021
• 作为产物：
  描述：

  [Fe2(CO)5(2-(mercaptomethyl)-2-methylpropane-1,3-dithiol(3-))][Fe2(CO)6L][LFe2(CO)6] 、 一氧化碳 以 二氯甲烷 为溶剂， 生成 [Fe2(CO)6(2-(mercaptomethyl)-2-methylpropane-1,3-dithiol(3-))]2[Fe2(CO)6]
  参考文献：
  名称：

  Synthesis, characterisation of two hexa-iron clusters with {Fe2S2(CO)x} (x=5 or 6) fragments and investigation into their inter-conversion

  摘要：

  Reaction of a trithiol ligand, 2-(mercaptomethyl)-2-methylpropane-1,3-dithiol (H(3)L), with tri-iron dodecacarbonyl in toluene produces two hexa-iron clusters ( 1 and 2). The two clusters are characterised crystallographically and spectroscopically. NMR spectroscopy reveals that the cluster 2 exists in two conformations in equilibrium 2(anti) double left right arrow 2(syn) and the equilibrium constant K(eq) = 0.55 under CO atmosphere. In the cluster 2, the central {Fe(2)S(2)(CO)(6)} sub-unit is flanked by two identical {Fe(2)S(2)(CO)(6)} satellite sub-units through thiolate linkages whereas one of the thiolate linkages can further form Fe-S bond with the proximal Fe atom in one of the two satellite sub-units to produce the cluster 1 by expelling one CO. This conversion can be entirely reversed by continuously purging CO through the solution of the cluster 1. As suggested by DFT calculations, the conversion features a key step, the rotation of the Fe(prox)(CO)(3) to expose a vacant site for exogenic ligand binding ( the S atom from the central sub-unit in this case) with concomitant switch for one of the three CO ligands in the unit of Fe(prox)(CO)(3) from terminal to bridging orientation. The conversion from the clusters 1-2 involving one CO uptake is much faster than its reverse process since the latter is an endergonic process characterised by large reaction barriers, as revealed by the DFT calculations. (C) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.09.021