| 143037-05-2

• CAS: 143037-05-2；143788-56-1
• 化学式: C₃₈H₃₁FeO₈P₂*K
• 分子量: 772.552
• InChiKey: ZZJBMMDLPUVNKY-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

• 作为产物：
  描述：

  cis-dihydrido-trans-bis(triphenylphosphite)dicarbonyliron 、 potassium hydride 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Ligand substitution processes on carbonylmetal derivatives. 2. Reaction of tetracarbonylhydridoferrates with phosphites

  摘要：

  Ligand substitution processes m KHFe(CO)4 (1) have been evidenced by reaction with various phosphites. The nature of the reaction products strongly depends on (i) the nature of the solvent, (ii) the Tolman cone angle of the phosphite, and (iii) the reaction conditions. In protic media (H2O-THF), phosphites with small cone angles, such as P(OMe)3, P(OEt)3, and P(OPh)3, react (2 equiv) with 1 at room temperature to give the corresponding complexes H2Fe(CO)2[P(OR)3]2 in > 90% yield, whereas a phosphite with a larger cons angle (P[O-o-C6H4Ph]3) reacts only at a higher temperature to afford the disubstituted Fe(CO)3[P{O-o-C6H4Ph}3]2 derivative in 94% yield. When the reaction with phosphites having small cone angles is conducted with a 3-fold excess of phosphite at 65-degree-C, the trisubtituted derivatives Fe(CO)2[P(OR)3]3 are formed in 75-96% yield. In aprotic medium (THF), 1 reacts with phosphites (2 equiv) at room temperature to yield the monosubstituted anionic hydrides K+[HFe(CO)3{P(OR)3}]-, which can be isolated in > 90% yield. In refluxing THF the reaction of 1 with P(OMe)3 (3 equiv) demonstrates the first synthesis of the hydridoferrate K+[HFe(CO)2{P(OMe)3}2]-. Protonation of K+[HFe(CO)3{P(OR)3}]-with trifluoroacetic acid in THF at -10-degrees-C provides an excellent route for the high-yield synthesis of the monosubstituted dihydrides H2Fe(CO)3[P(OR)3]. In situ reaction of the latter with another phosphane PZ3 (Z = Ph, OPh) leads to the mixed dihydrides H2Fe(CO)2[P(OR)3][PZ3] (R = Me, Et; Z = Ph, OPh), which are reported for the first time. Finally, reaction of H2Fe(CO)2[P(OEt)3]2 with KH under sonication allows the generation of the highly reduced derivative K2[Fe(CO)2{P(OEt)3}2], the first disubstituted analogue of the Collman reagent.

  DOI：

  10.1021/om00045a015

文献信息

• Synthesis and characterization of the electron-rich iron hydride HFe(CO)2(P(OPh)3)2- and its ligand-based redox substitution with thiolates
  作者：Marcetta Y. Darensbourg、Sheryl A. Wander、Joseph H. Reibenspies

  DOI：10.1021/om00046a012

  日期：1992.10

  The bis(phosphite) anionic hydride [Et4N+][HFe(CO)2(P(OPh)3)2-] has been synthesized by deprotonation of H2Fe(CO)2(P(OPh)3)2 with [Et4N+][OH-]. The [Et4N+][HFe(CO)2(P(OPh)3)2-] salt was characterized by X-ray diffraction, crystallizing in the monodinic space group Cc (No. 9) with a = 15.821 (4) angstrom, b = 15.168 (3) angstrom, c = 19.125 (5) angstrom, beta = 111.05 (2)-degrees, V = 4283 (2) angstrom3, and Z = 4. In the solid state the hydride anion has a distorted-trigonal-bipyramidal geometry in which the hydride ligand occupies an axial position with an Fe-H bond distance of 1.47 angstrom. One triphenyl phosphite ligand is cis to the hydride and has an Fe-P(eq) bond distance of 2.076 (1) angstrom, the other is trans with Fe-P(ax) = 2.083 (1) angstrom, and angle P(eq)-Fe-P(ax) is 103.2 (1)-degrees. Analysis of the nu(CO) infrared and H-1 NMR results imply that in solution the isomer in which both phosphite ligands are cis to the hydride predominates as the ground-state structure. The alkali-metal cations Na+ and K+ form contact ion pairs with [HFe(CO)2(P(OPh)3)2-], specifically interacting with the carbonyl oxygens of both CO ligands simultaneously. The [HFe(CO)2(P(OPh)3)2-] anion reacts with PhSSPh to yield [Et4N+][(PhS)Fe(CO)2(P(OPh)3)2-] but is unreactive with MeSSMe and t-BuSS-t-Bu.