[Fe2(ethanedithiolate)(CO)2(cis-1,2-bis(diphenylphosphino)ethene)] | 945735-89-7

• 英文名称: [Fe2(ethanedithiolate)(CO)2(cis-1,2-bis(diphenylphosphino)ethene)]
• 英文别名: Fe2(CO)2(S2C2H4)(cis-1,2-bis(diphenylphosphino)ethylene)2；Fe2(ethanedithiolate)(CO)2(cis-1,2-C2H2(PPh2)2)2；[Fe2(CO)2(ethanedithiolato)(cis-Ph2PCHCHPPh2)2]；Fe2(ethanedithiolate)(CO)2(dppv)2；[Fe2(CO)2(S2C2H4)(dppv)2]；Fe2(CO)2(S2C2H4)(dppv)2
• CAS: 945735-89-7
• 化学式: C₅₆H₄₈Fe₂O₂P₄S₂
• 分子量: 1052.72
• InChiKey: RPTXNBRRZAIXMM-FCFBSJPSSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  ferrocenium(III) tetrafluoroborate 、 [Fe2(ethanedithiolate)(CO)2(cis-1,2-bis(diphenylphosphino)ethene)] 以 二氯甲烷 为溶剂， 生成 [Fe2(CO)2(ethanedithiolato)(cis-Ph2PCHCHPPh2)2](BF4)2
  参考文献：
  名称：

  Diiron Dithiolato Carbonyls Related to the H_ox^CO State of [FeFe]-Hydrogenase

  摘要：

  Oxidation of the electron-rich (E-1/2 = -175 vs Ag/AgCl) ethanedithiolato complex Fe-2(S2C2H4)-(CO)(2)(dPPV)(2) (1) under a CO atmosphere yielded [Fe-2(S2C2H4)(mu-CO)(CO)(2)(dPPV)(2)](+) ([1(CO)](+)), a model for the H-ox(CO) state of the [FeFe]-hydrogenases. This complex exists as two isomers: a kinetically favored unsymmetrical derivative, unsym-[1(CO)](+), and a thermodynamically favored isomer, sym-[1(CO)](+), wherein both diphosphines span apical and basal sites. Crystallographic characterization of sym-[1(CO)](+) confirmed a C-2-symmetric structure with a bridging CO ligand and an elongated Fe-Fe bond of 2.7012(14) angstrom, as predicted previously. Oxidation of sym-[1(CO)](+) and unsym-[1(CO)](+) again by 1e(-) oxidation afforded the respective diamagnetic diferrous derivatives where the relative stabilities of the sym and unsym isomers are reversed. DFT calculations indicate that the stabilities of sym and unsym isomers are affected differently by the oxidation state of the diiron unit: the mutually trans CO ligands in the sym isomer are more destabilizing in the mixed-valence state than in the diferrous state. EPR analysis of mixed-valence complexes revealed that, for [1](+), the unpaired spin is localized on a single iron center, whereas for, unsymlsym[1(CO)](+), the unpaired spin was delocalized over both iron centers, as indicated by the magnitude of the hyperfine coupling to the phosphine ligands trans to the Fe-Fe vector. Oxidation of 1 by 2 equiv of acetylferrocenium afforded the dication [1](2+), which, on the basis of low-temperature IR spectrum, is structurally similar to [1](+). Treatment of [1](2+) with CO gives unsym-[1(CO)](2+).

  DOI：

  10.1021/ja7113008
• 作为产物：
  描述：

  Fe2(ethanedithiolate)(CO)4(cis-1,2-C2H2(PPh2)2) 、 顺-1,2-双(二苯基膦)乙烯 生成 [Fe2(ethanedithiolate)(CO)2(cis-1,2-bis(diphenylphosphino)ethene)]
  参考文献：
  名称：

  Lewis vs. Brønsted-basicities of diiron dithiolates: spectroscopic detection of the “rotated structure” and remarkable effects of ethane- vs. propanedithiolate

  摘要：

  新化合物Fe2(S2CnH2n)(CO)2(dppv)2（n = 2, 3；dppv = cis-1,2-C2H2(PPh2)2）与AlBr3和B(C6F5)3形成加合物，采用为纯铁氢酶活性位点提出的“旋转结构”——由于二硫醇带与Fe上的配体之间的非键相互作用，丙烷二硫醇的Lewis碱性明显增强。

  DOI：

  10.1039/b700754j

文献信息

• New Nitrosyl Derivatives of Diiron Dithiolates Related to the Active Site of the [FeFe]-Hydrogenases
  作者：Matthew T. Olsen、Aaron K. Justice、Frédéric Gloaguen、Thomas B. Rauchfuss、Scott R. Wilson

  DOI：10.1021/ic801542w

  日期：2008.12.15

  Nitrosyl derivatives of diiron dithiolato carbonyls have been prepared starting from the precursor Fe(2)(S(2)C(n)H(2n))(dppv)(CO)(4) (dppv = cis-1,2-bis(diphenylphosphinoethylene). These studies expand the range of substituted diiron(I) dithiolato carbonyl complexes. From [Fe(2)(S(2)C(2)H(4))(CO)(3)(dppv)(NO)]BF(4) ([1(CO)(3)]BF(4)), the following compounds were prepared: [1(CO)(2)(PMe(3))]BF(4), [1(CO)(dppv)]BF(4)

  当氰化物是亲核试剂时，亚硝酰基从 Fe(dppv) 位点迁移，产生 Fe(CN)(2)(NO) 衍生物。化合物 [1(CO)(3)]BF(4)、[1(CO)(2)(PMe(3))]BF(4) 和 [1(CO)(dppv)]BF(4) 是也可以通过将 NO(+) 添加到二、三和四取代的前体中来制备。在这些情况下，NO(+) 似乎形成一个初始的 36e(-) 加合物，其中包含终端 Fe-NO，然后是脱羰。通过向混合价 Fe(I)Fe(II) 衍生物中添加 NO 来制备几种配合物。二铁亚硝酰基配合物在温和电位下还原，在某些情况下与 CO 形成弱加合物。 1(CO)(dppv) 的 IR 和 EPR 光谱，由 [1(CO)(dppv)]BF(4) 的低温还原生成) 与 Co(C(5)Me(5))(2)，表明 SOMO 位于 FeNO 亚基上。亚硝酰基从 Fe(dppv) 位点迁移，产生 Fe(CN)(2)(NO)
• Terminal Hydride in [FeFe]-Hydrogenase Model Has Lower Potential for H₂ Production Than the Isomeric Bridging Hydride
  作者：Bryan E. Barton、Thomas B. Rauchfuss

  DOI：10.1021/ic800030y

  日期：2008.4.1

  Protonation of the symmetrical tetraphosphine complexes Fe2(S2CnH2n)(CO)2(dppv)2 afforded the corresponding terminal hydrides, establishing that even symmetrical diiron(I) dithiolates undergo protonation at terminal sites. The terminal hydride [HFe2(S2C3H6)(CO)2(dppv)2](+) was found to catalyze proton reduction at potentials 200 mV milder than the isomeric bridging hydride, thereby establishing a thermodynamic

  对称四膦配合物 Fe2(S2CnH2n)(CO)2(dppv)2 的质子化提供了相应的末端氢化物，确定即使是对称的二铁 (I) 二硫醇盐也在末端部位发生质子化。发现末端氢化物 [HFe2(S2C3H6)(CO)2(dppv)2](+) 在比异构桥连氢化物温和 200 mV 的电位下催化质子还原，从而建立了通过末端氢化物进行催化操作的热力学优势。氮杂二硫醇质子化得到[Fe2[(SCH2)2NH2](CO)2(dppv)2](+)、[HFe2[(SCH2)2NH](CO)2(dppv)2](+)和[ HFe2[(SCH2)2NH2](CO)2(dppv)2](2+)，取决于条件。