[Mo2(N-p-tolyl)2(S2P(OEt)2)2(μ-SCH2Ph)(μ-SO2)] | 177019-12-4

• 英文名称: [Mo2(N-p-tolyl)2(S2P(OEt)2)2(μ-SCH2Ph)(μ-SO2)]
• 英文别名: bis(p-tolylimido)-bis(diethyl dithiophosphato)-(μ-acetato)-dimolybdenum(V)-(μ-SBn)-(μ-SO2)
• CAS: 177019-12-4；176799-54-5
• 化学式: C₃₁H₄₄Mo₂N₂O₈P₂S₆
• 分子量: 1018.92
• InChiKey: DBNUPOSSLCUXDZ-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：

  [Mo2(N-p-tolyl)2(S2P(OEt)2)2(μ-SCH2Ph)(μ-SO2)] 以 氯仿 为溶剂， 以85%的产率得到[Mo2(N-p-tolyl)2(S2P(OEt)2)2(μ-SCH2Ph)(μ-O)]
  参考文献：
  名称：

  Oxidation at a Dimolybdenum(V) Sulfur Bridge. Formation of SO and SO₂ Bridges. Facile Extrusion of SO from the SO₂ Bridge

  摘要：

  Peroxide oxygenation of mu-thiolate-mu-sulfide Mo(V) dimer complexes of the type [Mo-2(NAr)(2)(S2P(OEt)(2))(2)(mu O(2)CMe)(mu-SR)(mu-S)] yielded Mo-2(mu-SO) and Mo-2(mu-SO2) complexes, demonstrating the reactivity sequence mu-S > mu-SO much greater than mu-SR. Inversion isomers of the pyramidal sulfur site in the mu-SO bridge were observed, and the pyramidicity was confirmed crystallographically. Visible light photolysis of the Mo-2(mu-SO2) complex liberated SO from the SO2 bridge and produced Mo-2(mu-O) compounds. Crystallography of analogous Mo-2(mu-S), Mo-2(mu-SO), Mo-2(mu-SO2), and Mo-2(mu-O) complexes provided structural comparisons related to variations in the bridge functionality. For 2, Mo2C31H44N2O6P2S6: a = 13.604(5) Angstrom, b = 15.280(4) Angstrom, c = 12.502(2) Angstrom, alpha = 93.36(2)degrees, beta = 112.00 (2)degrees, gamma = 76.01(2)degrees, triclinic, , Z = 2. For 3, Mo2C31H44N2O7P2S6: a = 12.535(2) Angstrom, b = 25.299(9) Angstrom, c = 13.989(5) Angstrom, beta = 99.99(2)degrees, monoclinic, P2(1)/n, Z = 4. For 4, Mo2C31H44N2O8PZS6: a = 12.591(9) Angstrom, b = 25.34(1) Angstrom, c = 14.048(3) Angstrom, beta = 100.79(4)degrees, monoclinic, P2(1)/n, Z = 4. For 5, Mo2C31H44N2O7P2S5: a = 13.731(5) Angstrom, b = 19.267(4) Angstrom, c = 16.652(5) Angstrom, beta = 104.78(3)degrees, monoclinic, P2(1)/n, Z = 4.

  DOI：

  10.1021/ic951518k
• 作为产物：
  描述：

  过氧乙酸 、 [Mo2(N-p-tolyl)2(S2P(OEt)2)2(μ-SCH2Ph)(μ-S)] 以 四氢呋喃 为溶剂， 以84%的产率得到[Mo2(N-p-tolyl)2(S2P(OEt)2)2(μ-SCH2Ph)(μ-SO2)]
  参考文献：
  名称：

  Oxidation at a Dimolybdenum(V) Sulfur Bridge. Formation of SO and SO₂ Bridges. Facile Extrusion of SO from the SO₂ Bridge

  摘要：

  Peroxide oxygenation of mu-thiolate-mu-sulfide Mo(V) dimer complexes of the type [Mo-2(NAr)(2)(S2P(OEt)(2))(2)(mu O(2)CMe)(mu-SR)(mu-S)] yielded Mo-2(mu-SO) and Mo-2(mu-SO2) complexes, demonstrating the reactivity sequence mu-S > mu-SO much greater than mu-SR. Inversion isomers of the pyramidal sulfur site in the mu-SO bridge were observed, and the pyramidicity was confirmed crystallographically. Visible light photolysis of the Mo-2(mu-SO2) complex liberated SO from the SO2 bridge and produced Mo-2(mu-O) compounds. Crystallography of analogous Mo-2(mu-S), Mo-2(mu-SO), Mo-2(mu-SO2), and Mo-2(mu-O) complexes provided structural comparisons related to variations in the bridge functionality. For 2, Mo2C31H44N2O6P2S6: a = 13.604(5) Angstrom, b = 15.280(4) Angstrom, c = 12.502(2) Angstrom, alpha = 93.36(2)degrees, beta = 112.00 (2)degrees, gamma = 76.01(2)degrees, triclinic, , Z = 2. For 3, Mo2C31H44N2O7P2S6: a = 12.535(2) Angstrom, b = 25.299(9) Angstrom, c = 13.989(5) Angstrom, beta = 99.99(2)degrees, monoclinic, P2(1)/n, Z = 4. For 4, Mo2C31H44N2O8PZS6: a = 12.591(9) Angstrom, b = 25.34(1) Angstrom, c = 14.048(3) Angstrom, beta = 100.79(4)degrees, monoclinic, P2(1)/n, Z = 4. For 5, Mo2C31H44N2O7P2S5: a = 13.731(5) Angstrom, b = 19.267(4) Angstrom, c = 16.652(5) Angstrom, beta = 104.78(3)degrees, monoclinic, P2(1)/n, Z = 4.

  DOI：

  10.1021/ic951518k

文献信息

• Alkylation of a Dimolybdenum SO Bridge, Subsequent Reactions, and Characterization of the Thioperoxide Bridge
  作者：Chi Minh Tuong、Whitney K. Hammons、Ashley L. Howarth、Kelly E. Lutz、Ackim D. Maduvu、Laura B. Haysley、Brian R. T. Allred、Lenore K. Hoyt、Mark S. Mashuta、Mark E. Noble

  DOI：10.1021/ic9002093

  日期：2009.6.1

  The SO bridge of the complex, [Mo2(NTo)2(S2P(OEt)2)2(μ-O2CMe)(μ-SBn)(μ-SO)], 1, displayed nucleophilicity at O, giving alkylation products [Mo2(NTo)2(S2P(OEt)2)2(μ-O2CMe)(μ-SBn)(μ-SOR)]+, 4+, which contained the thioperoxide bridge. These cations were then subject to nucleophilic attack by two pathways. Debenzylation of the bridge thiolate in 4+ afforded neutral [Mo2(NTo)2(S2P(OEt)2)2(μ-O2CMe)(μ-S)(μ-SOR)]

  该复合物的SO桥，[沫2（NTO）2（š 2 P（OET）2）2（μ-O 2 CME）（μ-SBN）（μ-SO）]，1，显示亲核性在O，给烷基化产物[沫2（NTO）2（S 2 P（OET）2）2（μ-O 2 CME）（μ-SBN）（μ-SOR）] +，4 +，其中载有thioperoxide桥。然后，这些阳离子通过两种途径受到亲核攻击。硫醇桥在4 +中的脱苄基反应得到中性[Mo 2（NTo）2（S 2 P（OET）2）2（μ-O 2 CME）（μ-S）（μ-SOR）]，5 ; 在二硫代磷酸酯配体的脱酯化4 +，得到[沫2（NTO）2（š 2 P（= O）（OET））（S 2 P（OET）2）（μ-O 2 CME）（μ-SBn的）（μ-SO）]，6，其中包含单酯二硫代磷酸酯配体。综合大楼1在结晶状态下产生缓慢而干净的反应，通过攻击晶格中的相邻分子进一步证明了其亲核性。X射线晶体学证实了硫代过氧化物键并揭示了Mo