Mo3(μ3-S)(μ-S)3(μ-diethyl dithiophosphate)(diethyl dithiophosphate)3(CH3CN) | 159767-03-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子
• 英文名称: Mo3(μ3-S)(μ-S)3(μ-diethyl dithiophosphate)(diethyl dithiophosphate)3(CH3CN)
• CAS: 159767-03-0
• 化学式: C₁₈H₄₃Mo₃NO₈P₄S₁₂
• 分子量: 1198.05
• InChiKey: AHAKAAFWPBNZNR-UHFFFAOYSA-J

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：

  Mo3(μ3-S)(μ-S)3(μ-diethyl dithiophosphate)(diethyl dithiophosphate)3(CH3CN) 在 acetic anhydride 、 pyridine 作用下， 以 乙醇 为溶剂， 以40%的产率得到Mo3(μ3-S)(μ-S)3(diethyl dithiophosphate)3(μ-O2CCH3)(pyridine)
  参考文献：
  名称：

  Yao, Yuangen; Akashi, Haruo; Sakane, Genta, Inorganic Chemistry, 1995, vol. 34, # 1, p. 42 - 48

  摘要：

  DOI：
• 作为产物：
  描述：

  tetraphosphorus decasulfide 、 乙腈 在 Mo₃S₄⁽⁴⁺⁾(aq) 、 EtOH 作用下， 以 盐酸 、 乙醇 为溶剂， 以82%的产率得到Mo3(μ3-S)(μ-S)3(μ-diethyl dithiophosphate)(diethyl dithiophosphate)3(CH3CN)
  参考文献：
  名称：

  Yao, Yuangen; Akashi, Haruo; Sakane, Genta, Inorganic Chemistry, 1995, vol. 34, # 1, p. 42 - 48

  摘要：

  DOI：

文献信息

• Redox Properties and Catalytic Ability toward Electrochemical Proton Reduction of Sulfur-Bridged Trinuclear Mo₃S₄ Complexes Containing Acetate, Trifluoroacetate, and/or Dithiophosphate as Bridging Ligands
  作者：Keisuke Kawamoto、Akio Ichimura、Hideki Hashimoto、Isamu Kinoshita、Masakazu Hirotsu、Takanori Nishioka

  DOI：10.1246/bcsj.20140364

  日期：2015.4.15

  A novel complex with the terminal acetonitrile and bridging trifluoroacetate (tfa) ligands of [Mo3S4(dtp)3(μ-tfa)(NCCH3)] (dtp: diethyl dithiophospate) (1-tfa) was prepared from the substitution reaction of [Mo3S4(dtp)3(μ-dtp)(NCCH3)] (1-dtp) with trifluoroacetate anhydride in acetonitrile. The reaction of 1-dtp with trifluoroacetic acid in dichloromethane also afforded 1-tfa. Complex 1-tfa reacts with pyridine in ethanol resulting in the formation of a complex with the terminal pyridine ligand (py), [Mo3S4(dtp)3(μ-tfa)(py)] (2-tfa). Structures of 1-tfa and 2-tfa were determined by single-crystal X-ray structural analysis showing that one of three Mo–Mo distances depend on a kind of the bridging ligands, dtp, OAc, and tfa, while no trends in the other two Mo–Mo distances in each of the complexes with the different bridging ligands. Each of the cyclic voltammograms of 1-dtp, [Mo3S4(dtp)3(μ-OAc)(NCCH3)] (OAc: acetate) (1-OAc), 1-tfa, [Mo3S4(dtp)3(μ-OAc)(py)] (2-OAc), and 2-tfa showed two consecutive one-electron reduction waves and an oxidation wave, which are formally assigned to the Mo(IV IV IV)/Mo(III IV IV), Mo(III IV IV)/Mo(III III IV), and Mo(V IV IV)/Mo(IV IV IV) couples, respectively. The re-oxidation and re-reduction peaks for the second reduction and the oxidation processes were not observed for all of the complexes. The redox potentials of the first reduction processes were shifted up to ca. 200 mV with the bridging and terminal ligands, for example, the redox potentials appeared at −0.98 and −1.19 V vs. Fc/Fc+2-OAc and 1-tfa, respectively, due to the lower electron-donating ability of CH3CN and tfa ligands compared to that of the py and OAc ligands. The re-oxidation peak for the second reduction process of 2-OAc was observed at −80 °C suggesting that this is an EC process and the chemical reaction following the second electrochemical reduction is probably inhibited at low temperature. On the other hand, no re-reduction peak for the oxidation process appeared even at −80 °C implying that the oxidation process is accompanied by a significant structural change. This argument is supported by the results of the DFT calculation. The HOMO component of the complex contains a bonding character between the two acetate-bridged Mo centers and the other acetate-unbridged one, and the spin densities of the 1-electron oxidized complex mostly located at the one of two acetate-bridged Mo centers and the other acetate-unbridged one. Cyclic voltammograms of these complexes in the presence of trifluoroacetic acid as a proton source exhibited catalytic currents around the first reduction wave for each complex. The DFT calculations for 2-OAc and 2-tfa demonstrated that the HOMO components are also distributed over the doubly bridged sulfur ligands in addition to the Mo centers in the Mo3S4 core. These result suggests that a protonation reaction of 2-OAc and 2-tfa probably occurs on the doubly bridged sulfur ligand in the Mo3S4 core.

  [MO3S4(dtp)3(μ-tfa)(NCCH3)]（dtp：二硫代磷酸盐二乙酯）（1-tfa）与三氟乙酸酐在乙腈中发生置换反应，制备出一种具有乙腈末端和桥接三氟乙酸酐（tfa）配体的新型配合物。1-dtp 与三氟乙酸在二氯甲烷中的反应也得到了 1-tfa。络合物 1-tfa 在乙醇中与吡啶反应，形成了一个带有末端吡啶配体（py）的络合物 [MO3S4(dtp)3(μ-tfa)(py)]（2-tfa）。通过单晶 X 射线结构分析确定了 1-tfa 和 2-tfa 的结构，结果表明三种 MO-MO 间距中的一种取决于一种桥接配体（dtp、OAc 和 tfa），而在具有不同桥接配体的每个配合物中，其他两种 MO-MO 间距没有变化趋势。1-dtp、[MO3S4(dtp)3(μ-OAc)(NCCH3)]（OAc：醋酸盐）（1-OAc）、1-tfa、[MO3S4(dtp)3(μ-OAc)(py)]（2-OAc）和 2-tfa 显示了两个连续的单电子还原波和一个氧化波，它们分别被正式归属于 MO(IV IV)/MO(III IV IV)、MO(III IV IV)/MO(III III IV)和 MO(V IV IV)/MO(IV IV)偶。所有配合物都没有观察到第二次还原和氧化过程的再氧化和再还原峰。第一还原过程的氧化还原电位随桥接配体和末端配体的变化而移动，最高可达约 200 mV，例如，与 Fc/Fc+2-OAc 和 1-tfa 相比，氧化还原电位分别为-0.98 V 和-1.19 V，这是因为 CH3CN 和 tfa 配体的电子负载能力低于 py 和 OAc 配体。2-OAc 第二次还原过程的再氧化峰在 -80 ℃ 下出现，这表明这是一个电化学还原过程，第二次电化学还原后的化学反应可能在低温下受到抑制。另一方面，即使在 -80 ℃ 下也没有出现氧化过程的再还原峰，这意味着氧化过程伴随着显著的结构变化。这一论点得到了 DFT 计算结果的支持。络合物的 HOMO 分量包含两个醋酸桥 MO 中心和另一个醋酸未桥中心之间的成键特性，而 1 电子氧化络合物的自旋密度大多位于两个醋酸桥 MO 中心之一和另一个醋酸未桥中心。在以三氟乙酸为质子源的条件下，这些复合物的循环伏安图显示了每个复合物在第一个还原波附近的催化电流。2-OAc 和 2-tfa 的 DFT 计算表明，除了 MO3S4 核心中的钼中心外，HOMO 成分还分布在双桥硫配体上。这些结果表明，2-OAc 和 2-tfa 的质子化反应可能发生在 MO3S4 核心的双桥硫配体上。