| 528818-58-8

• CAS: 528818-58-8
• 化学式: C₂₀H₁₂FeO₂S₄
• 分子量: 468.425
• InChiKey: ZKHNMQYLVIZBGF-UHFFFAOYSA-L

反应信息

• 作为产物：
  描述：

  以 四氢呋喃 、 甲醇 为溶剂， 生成
  参考文献：
  名称：

  具有刚性 [Fe('tpS4'] 核和 σ−π 共配体 ('tpS4'2 = 1,2) 的富硫 [Fe(L1)(L2)('tpS4')] 配合物的合成、结构和反应性-双(2-巯基苯硫基)亚苯基(2-)；L1, L2 = CO, PR3, NO)

  摘要：

  合成和纯化步骤的优化使得新配体“tpS4”2- 可以制备量使用。用 'tpS4'-Li2 或 'tpS4'-Na2 处理 FeCl2·4H2O 产生 [Fe('tpS4')] (1)，它在固态和没有共配体的情况下可能三聚化以产生顺磁性 [Fe ('tpS4')]3. [Fe('tpS4')] 片段显示出 'tpS4'2− 配体的螺旋配位，并结合 σ−π 配体，如 CO、NO 和磷烷，得到通式 [Fe(L1 )(L2)('tpS4')]。顺式二羰基络合物 [Fe(CO)2('tpS4')] (2) 是不稳定的，很容易将 CO 解离成双核 [Fe(CO)('tpS4')]2 (3)。CO 和磷烷的同时配位产生 [Fe(CO)(PR3)('tpS4')]，其中 R = Me (4)、Et (5)、Pr (6) 和 Bu (7)，但事实证明，不可能获得具有庞大 PPh3 或 PCy3 配体的类似配合物。双（磷烷）配合物只能用

  DOI：

  10.1002/ejic.200390058

文献信息

• Transition metal complexes with sulfur ligands. Part CLV.11For Part CLIV see Ref. [1], Eur. J. Inorg. Chem., in press. Structural and spectroscopic characterization of hydrogen bridge diastereomers of [μ-N2H2{Fe(PR3)(‘tpS4’)}2] diazene complexes (‘tpS4’2−=1,2-bis(2-mercaptophenylthio)phenylene(2−))
  作者：Dieter Sellmann、David C.F Blum、Frank W Heinemann

  DOI：10.1016/s0020-1693(02)00987-8

  日期：2002.9

  New diazene complexes of the type [mu-N2H2 Fe(PR3)('tPS(4)'))(2)] (R = Pr (1), Bu (2)) have been synthesized from FeCl2.4H(2)O, PR3, 'tpS(4),(2-) in THF-MeOH solution and N2H2 generated in situ by hydrolysis of K2N2(CO2)(2) with acetic acid. The deuterated complexes [mu-N2D2Fe(PR3)('tPS(4)')}(2)] (R = Pr (3), Bu (4)) were obtained by using D2O, CH3OD and CH3CO2D. The complexes 1-4 each form as a mixture of two diastereomers. Fractional crystallization of I from either toluene or CH2Cl2 afforded single crystals of 1a.2toluene and 1b.4CH(2)Cl(2) that were characterized by X-ray structure determination and permitted to establish unambiguously the hydrogen bridge diastereoisomerism of 1a and 1b. Complexes 1a and 1b differ from each other mainly with respect to the orientation of N-H...S(thiolate) bridges, but are nearly identical otherwise. The reactivity of 1-4 was investigated with respect to H+/D+ exchange, reversible oxidation and PR3 exchange reactions. The PPr3 ligands of 1 can be exchanged reversibly for PBu3 to give 2 under retention of the [Fe-NH=NH-Fe] cores. The PR3 exchange is rationalized by dissociation of the PR3 ligands yielding intermediates with five-coordinate iron centers. Such intermediates also account for the isomerization of 1a and 1b and related diazene complexes, for which a mechanism is proposed. (C) 2002 Elsevier,Science B.V. All rights reserved.