[Ru^II(4′-(4-methylmercaptophenyl)-2,2′:6′2″-terpyridine)(DMSO)Cl2] | 1582781-58-5

• 英文名称: [Ru^II(4′-(4-methylmercaptophenyl)-2,2′:6′2″-terpyridine)(DMSO)Cl2]
• CAS: 1582781-58-5
• 化学式: C₂₄H₂₃Cl₂N₃ORuS₂
• 分子量: 605.574
• InChiKey: MJVIJXFEBHLOFP-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：

  ammonium hexafluorophosphate 、 2,2'-联吡啶-4,4'-二甲酸甲酯 、 [Ru^II(4′-(4-methylmercaptophenyl)-2,2′:6′2″-terpyridine)(DMSO)Cl2] 在 三乙胺 作用下， 以 甲醇 为溶剂， 以58%的产率得到[Ru^II(MeMPTP)(dmcbpy)Cl]PF₆
  参考文献：
  名称：

  [Ru（terpy）（bipy）Cl] +配合物的合成，晶体结构和水氧化活性：辅助配体对O 2生成的影响†

  摘要：

  四个新的Ru（II）络合物，[Ru II（MeMPTP）（bpy）Cl] PF 6（1），[Ru II（MeMPTP）（dmbpy）Cl] PF 6（2），[Ru II（MeMPTP）（dmcbpy） ）Cl] PF 6（3）和[Ru II（MeMPTP）（Pic）2 Cl] PF 6（4）[其中，MeMPTP = 4'-（4-甲基巯基苯基）-2,2'：6'2'' -叔吡啶，bpy = 2,2'-联吡啶，dmbpy = 4,4'-二甲基-2,2'-联吡啶，dmcbpy = 4,4'-二甲氧基羰基-2,2'-联吡啶，pic = 4-甲基吡啶]通过合成和表征各种光谱技术。配合物1和2的分子结构通过单晶X射线衍射分析确定。配合物1-4的水化学氧化催化活性表明O 2的释放速率遵循1 > 4 > 2 > 3的趋势。除了未取代的复杂1，用于O-催化速率2代的2和4，含有供电子性（-CH 3）基团，比的

  DOI：

  10.1039/c7ra07186h
• 作为产物：
  描述：

  dichlorotetrakis(dimethylsulfoxide)ruthenium(II) 、 4′-(4-methylmercaptophenyl)-2,2′:6′2″-terpyridine 以 甲醇 为溶剂， 反应 7.0h， 以58%的产率得到[Ru^II(4′-(4-methylmercaptophenyl)-2,2′:6′2″-terpyridine)(DMSO)Cl2]
  参考文献：
  名称：

  Effect of Substituents on the Water Oxidation Activity of [Ru^II(terpy)(phen)Cl]⁺ Procatalysts

  摘要：

  A series of [Ru-II(terpy-R)(phen-X)Cl]PF6 complexes was designed where terpy-R is the tridentate 4'-(4-methylmercaptophenyl)-2,2':6'2"-terpyridine ligand MeMPTP and phen-X is a substituted phenanthroline with hydro (I), 5-nitro (2), 5,6-dimethyl (3), and 3,4,7,8-tetramethyl (4). This series allows us to compare the reactivity of phenanthroline-containing procatalysts with that of its well-established bipyridine counterparts as well as to study the effects of electron-withdrawing and -donating substituents on water oxidation. These species were thoroughly characterized by spectroscopic and spectrometric methods, and the structures of 1, 3, and 4 were determined by single-crystal X-ray diffraction. The procatalysts 1-4 show opposite trends compared to known terpyridine/bipyridine species; the unsubstituted procatalyst 1 yields a turnover number (TON) of 410 followed by 250 and 150 for complexes 3 and 4 with electron-donating substituents. Species 2, with electron-withdrawing properties, yields the lowest TON of 60. Although the TONs decrease upon substitution, the presence of electron-donating methyl substituents enhances the rate of O-2 evolution during an early stage of catalysis. Interestingly, no evidence of conversion from chlorido-containing procatalysts into expected aqua-containing catalysts was observed for 1-4 by NMR and UV-visible spectroscopy during the induction period. This observation, along with reactivity toward (NH4)(2)[Ce-IV(NO3)(6)], suggests that water nucleophilic attack happens to a high-valent ruthenium species rather than while at the Re oxidation state. Reactivity follows a trend similar to the rate of O-2 evolution in all complexes. Furthermore, the electrospray ionization mass spectrometry and H-1 NMR analyses of 1, as recovered after catalysis, indicate the presence of a chlorido ligand.

  DOI：

  10.1021/ic402118u