Fe[Ph₂P-2-C₆H₄CH=NC₆H₄Cl](CO)₃ | 1394246-09-3

• 英文名称: Fe[Ph₂P-2-C₆H₄CH=NC₆H₄Cl](CO)₃
• CAS: 1394246-09-3
• 化学式: C₂₈H₁₉ClFeNO₃P
• 分子量: 539.738
• InChiKey: ZDAQXIIMDBGSHJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 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 、 Fe[Ph₂P-2-C₆H₄CH=NC₆H₄Cl](CO)₃ 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  铁羰基的氨基-膦配合物中以胺为中心的反应

  摘要：

  Fundamental reactions of imino-phosphine ligands were elucidated through studies on Ph2PC6H4CH=NC6H4-4-Cl (PCHNArCl) complexes of iron(0), iron(I), and iron(II). The reaction of PCHNArCl with Fe(bda)(CO)(3) gives Fe(PCHNArCl)(CO)(3) (1), featuring an eta(2)-imine. DNMR studies, its optical properties, and DFT calculations suggest that 1 racemizes on the NMR time scale via an achiral N-bonded imine intermediate. The N-imine isomer is more stable in Fe(PCHNArOMe)(CO)(3) (1(OMe)), which crystallized despite being the minor isomer in solution. Protonation of 1 by HBF4Et2O gave the iminium complex [1H]BF4. The related diphosphine complex Fe(PCHNArCl)(PMe3)(CO)(2) (2), which features an eta(2)-imine, was shown to also undergo N protonation. Oxidation of 1 and 2 with FcBF(4) gave the Fe(I) compounds [1]BF4 and [2]BF4. The oxidation-induced change in hapticity of the imine from eta(2) in [1](0) to kappa(1) in [1](+) was verified crystallographically. Substitution of a CO ligand in 1 with PCHNArCl gave Fe[P-2(NArCl)(2)](CO)(2) (3), which contains the tetradentate diamidodiphosphine ligand. This C-C coupling is reversed by chemical oxidation of 3 with FcOTf. The oxidized product of [Fe(PCHNArCl)(2)(CO)(2)](2+) ([4](2+)) was prepared independently by the reaction of [1](+), PCHNArCl, and Fc(+). The C-C scission is proposed to proceed concomitantly with the reduction of Fe(II) via an intermediate related to [2](+).

  DOI：

  10.1021/acs.organomet.6b00318
• 作为产物：
  描述：

  Fe[Ph₂P-2-C₆H₄CH=NC₆H₄Cl](CO)₄ 生成 Fe[Ph₂P-2-C₆H₄CH=NC₆H₄Cl](CO)₃
  参考文献：
  名称：

  C 2-对称的铁（II）二膦-二烷氧基二羰基化合物及相关配合物

  摘要：

  Fe（bda）（CO）3（bda =苄叉基丙酮）与Ph 2 P-2-C 6 H 4 CHO（PCHO）反应，制得双膦双醇盐配合物Fe [（Ph 2 PC 6 H 4）2 C 2 H 2 O 2 ]（CO）2（1）由两个甲酰基与Fe（0）氧化为Fe（II）的头对头偶联而产生。晶体学研究表明1具有反式转化为CO的顺式烷氧基配体。两个膦基是相互反式的P–Fe–P角度为167.44（4）°。从加合物Fe（PCHO）（CO）4（2）开始检查通向1的途径，该加合物是通过将PCHO加到Fe 2（CO）9中获得的。化合物2 decarbonylates，得到三羰基铁（κ 1，η 2 -PCHO）（CO）3（3），其特点是π键合的醛。的光解2给出的混合物3和异构体氢化HFE（κ 2 -PCO）（CO）3。配合物3与另外等价的PCHO反应生成1，而用PPH治疗3，得到取代产物的Fe（κ 1，η 2 -PCHO）（PPH

  DOI：

  10.1021/om300631a