[Ru(II)(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)2(2-(2'-pyridyl)imidazole)(1-)] | 1003017-43-3

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [Ru(II)(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)2(2-(2'-pyridyl)imidazole)(1-)]
• 英文别名: [Ru(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)2(2-(2'-pyridyl)imidazole(-1H))]
• CAS: 1003017-43-3
• 化学式: C₁₈H₈F₁₂N₃O₄Ru
• 分子量: 659.33
• InChiKey: YGKKAPJINVGKTP-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：

  1-羟基-2,2,6,6-四甲基哌啶 、 [Ru(II)(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)2(2-(2'-pyridyl)imidazole)(1-)] 以 氘代乙腈 为溶剂， 生成 [Ru(II)(1,1,1-5,5,5-hexafluoro-2,4-pentanedionato)2(2-(2'-pyridyl)imidazole)]
  参考文献：
  名称：

  用于氢原子转移的双（β-二酮）钌吡啶-咪唑配合物的合成和表征。

  摘要：

  双（β-二酮）钌配合物已在 RuII 和 RuIII 氧化水平下与质子化和去质子化的吡啶-咪唑配体制备。RuII(acac)2(py-imH) (1)、[RuIII(acac)2(py-imH)]OTf (2)、RuIII(acac)2(py-im) (3)、RuII(hfac)2 (py-imH) (4) 和 [DBU-H][RuII(hfac)2(py-im)] (5) 已得到充分表征，包括 X 射线晶体结构（acac = 2,4-pentanedionato， hfac = 1,1,1,5,5,5-六氟-2,4-戊二酮，py-imH = 2-(2'-吡啶基)咪唑，DBU = 1,8-二氮杂双环[5.4.0]十一碳- 7-烯）。对于 acac-咪唑配合物 1 和 2，MeCN 中的循环伏安法显示 RuIII/II 还原电位 (E1/2) 相对于 Cp2Fe+/0 为 -0.64 V。去质子化咪唑复合物

  DOI：

  10.1021/ic7015726
• 作为产物：
  描述：

  [1,8-diazabicyclo[5.4.0]undec-7-ene(+1H)][Ru(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)2(2-(2'-pyridyl)imidazole(-1H))] 在 tri-p-tolylaminium hexafluorophophate 作用下， 以 氘代乙腈 为溶剂， 生成 [Ru(II)(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)2(2-(2'-pyridyl)imidazole)(1-)]
  参考文献：
  名称：

  用于氢原子转移的双（β-二酮）钌吡啶-咪唑配合物的合成和表征。

  摘要：

  双（β-二酮）钌配合物已在 RuII 和 RuIII 氧化水平下与质子化和去质子化的吡啶-咪唑配体制备。RuII(acac)2(py-imH) (1)、[RuIII(acac)2(py-imH)]OTf (2)、RuIII(acac)2(py-im) (3)、RuII(hfac)2 (py-imH) (4) 和 [DBU-H][RuII(hfac)2(py-im)] (5) 已得到充分表征，包括 X 射线晶体结构（acac = 2,4-pentanedionato， hfac = 1,1,1,5,5,5-六氟-2,4-戊二酮，py-imH = 2-(2'-吡啶基)咪唑，DBU = 1,8-二氮杂双环[5.4.0]十一碳- 7-烯）。对于 acac-咪唑配合物 1 和 2，MeCN 中的循环伏安法显示 RuIII/II 还原电位 (E1/2) 相对于 Cp2Fe+/0 为 -0.64 V。去质子化咪唑复合物

  DOI：

  10.1021/ic7015726

文献信息

• Trends in Ground-State Entropies for Transition Metal Based Hydrogen Atom Transfer Reactions
  作者：Elizabeth A. Mader、Virginia W. Manner、Todd F. Markle、Adam Wu、James A. Franz、James M. Mayer

  DOI：10.1021/ja8081846

  日期：2009.4.1

  Reported herein are thermochermical studies of hydrogen atom transfer (HAT) reactions involving transition metal H-atom donors (MLH)-L-II and oxyl radicals. [Fe-II(H(2)bip)(3)](2+), [Fe-II(H(2)bim)(3)](2+), (Co-II(H(2)bim)(3))(2+), and Ru-II(acac)(2)(py-imH) [H(2)bip = 2,2'-bi-1,4,5,6-tetrahydropyrimidine, H(2)bim = 2,2'-bi-imidazoline, acac = 2,4-pentandionato, py-imH = 2-(2'-pyridyl)imidazole)] each react with TEMPO (2,2,6,6-tetramethy-1-piperidinoxyl) or (Bu3PhO center dot)-Bu-t (2,4,6-tri-tert-butylphenoxyl) to give the deprotonated, oxidized metal complex (ML)-L-III and TEMPOH or (Bu3PhOH)-Bu-t. Solution equilibrium measurements for the reaction of [Co-II(H(2)bim)(2+) with TEMPO show a large, negative ground-state entropy for hydrogen atom transfer, -41 +/- 2 cal mol(-1) K-1. This is even more negative than the Delta S degrees(HAT) = -30 +/- 2 cal mol(-1) K-1 for the two iron complexes and the Delta S degrees(HAT) for Ru-II(acac)(2)(py-imH) + TEMPO, 4.9 +/- 1.1 cal mol(-1) K-1, as reported earlier. Calorimetric measurements quantitatively confirm the enthalpy of reaction for [Fe-II(H(2)bip)(3)](2+) + TEMPO, thus also confirming Delta S degrees(HAT). Calorimetry on TEMPOH + (Bu3PhO center dot)-Bu-t gives Delta H degrees(HAT) = -11.2 +/- 0.5 kcal mol(-1) which matches the enthalpy predicted from the difference in literature solution BDEs. A brief evaluation of the literature thermochemistry of TEMPOH and (Bu3PhOH)-Bu-t supports the common assumption that I Delta S degrees(HAT) approximate to 0 for HAT reactions of organic and small gas-phase molecules. However, this assumption does not hold for transition metal based HAT reactions. The trend in magnitude of I Delta S degrees I-HAT for reactions with TEMPO, Ru-II(acac)(2)(Py-imH) << (Fe-II(H(2)bip)(3)](2+) = [Fe-II(H(2)bim)(3)](2+) < [Co(II)bim)(3)](2+), is surprisingly well predicted by the trends for electron transfer half-reaction entropies, Delta S degrees(ET), in aprotic solvents. This is because both Delta S degrees(ET) and Delta S degrees(HAT) have substantial contributions from vibrational entropy, which varies significantly with the metal center involved. The close connection between Delta S degrees(HAT) and Delta S degrees(ET) provides an important link between these two fields and provides a starting point from which to predict which HAT systems will have important ground-state entropy effects.