| 138606-25-4

• CAS: 138606-25-4
• 化学式: C₂₆H₃₃FeO₂P₃
• 分子量: 526.315
• InChiKey: SXYOTFFSHUGMIS-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  cis-dihydrido-trans-bis(dimethylphenylphosphine)dicarbonyliron 、 二甲基苯基磷 以 乙醇 为溶剂， 生成
  参考文献：
  名称：

  Ligand substitution processes on carbonylmetal derivatives. 1. Reaction of tetracarbonylhydridoferrates with phosphines

  摘要：

  Ligand substitution processes on KHFe(CO)4 (1) have been demonstrated for the first time by reaction with various phosphines (2 equiv). The reaction times and the nature of the reaction products strongly depend on (i) the nature of the solvent, (ii) the cone angle of the phosphine, and (iii) the reaction conditions. In protic media (e.g. EtOH), phosphines with small cone angles (P(n-Bu)3, PMe2Ph) react with 1 below room temperature to give the newly characterized H2Fe(CO)2(PR3)2 in good yield, whereas phosphines with larger cone angles react only at higher temperature and afford the disubstituted Fe(CO)3(PR3)2 derivatives in quantitative yield. In aprotic medium (THF), phosphines (P(n-Bu)3, PPh3) react only slowly with 1 at room temperature but do so at reflux temperature to yield K2Fe(CO)4 (50%) and bis- or tris-(phosphine)carbonyliron derivatives. The reaction mechanism involves the formation of a monosubstituted K+[HFe(CO)3(PR3)- derivative with a rate strongly dependent on the Tolman cone angle of the phosphine. In THF, this basic hydrido carbonyl anion reacts with 1 to yield K2Fe(CO)4 and H2Fe(CO)3(PR3). The latter further reacts to give bis- or tris(phosphine)carbonyliron derivatives. In ethanol, the monosubstituted K+[HFe(CO)3(PR3)]- derivative is protonated to give the neutral dihydride H2Fe(CO)3(PR3), which, depending on the reaction conditions, is converted either to H2Fe(CO)2(PR3)2 by CO substitution (at low temperature) or to Fe(CO)3(PR3)2 by H-2 elimination (at higher temperature). For phosphines exhibiting small cone angles, the disubstituted dihydride may react further with an excess of phosphine to yield the trisubstituted Fe(CO)2(PR3)3 derivative in good yield.

  DOI：

  10.1021/om00039a045

文献信息

• Kinetic studies on the reactions of the tricarbonyl(1–3,6-η-cyclo-octadiene)-iron and -ruthenium complexes with tertiary phosphines and phosphites
  作者：Brian F. G. Johnson、Jack Lewis、Martyn V. Twigg

  DOI：10.1039/dt9740000241

  日期：——

  6-η-cyclo-octadiene), (Ia), when treated with tertiary phosphines L (L = triphenylphosphine or triphenyl phosphite) in n-heptane (40–70 °C) produces the monosubstituted derivative [(1–3,6-η-C8H12)Fe(CO)2L], (IIa), via a CO-dissociative mechanism. Observed pseudo-first-order rate constants for reaction with a range of more nucleophilic phosphorus ligands (for example methyl phosphite) are given by the relation kobs=k1+k2[L]

  的配合物[（1-3,6-η-C 8 H ^ 12）的Fe（CO）3 ]（1-3,6-η-C 8 H ^ 12 = 1-3,6-η -环辛二烯）， （Ia）中，当用在正庚烷（40-70℃）的叔膦L（L =三苯基膦或亚磷酸三苯酯）处理产生的单取代的衍生物[（1-3,6-η-C 8 H ^ 12）的Fe（ （CO）2 L]，（IIa），通过CO-解离机理。通过与关系式k obs = k 1 + k 2给出与一系列更多亲核性磷配体（例如亚磷酸甲酯）反应的观察到的拟一级反应速率常数。[L]。与配体无关的术语对应于羰基取代的衍生物的形成，而与配体无关的术语对应于络合物[Fe（CO）2 L 3 ]，（IIa）和反式环酮C 9 H 12 O的形成。 ，（III）。对类似钌体系的研究表明，CO的分解（在40°C时）约为。比铁络合物大40倍。这是由于更有利的活化焓引起的。但是，尚未检测到该络合物的二阶反应。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Fe: Org.Verb.B1, 1.1.4.2.1, page 94 - 100
  作者：

  DOI：——

  日期：——