trans-[Fe(NC5H4(NHP(i-Pr)2)2)(CO)2Cl]O3SCF3 | 1228019-90-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: trans-[Fe(NC5H4(NHP(i-Pr)2)2)(CO)2Cl]O3SCF3
• 英文别名: trans-[Fe(PNP-iPr)(CO)2Cl][CF3SO3]；2-N,6-N-bis[di(propan-2-yl)phosphanyl]pyridine-2,6-diamine;carbon monoxide;iron(2+);trifluoromethanesulfonate;chloride
• CAS: 1228019-90-6
• 化学式: CF₃O₃S*C₁₉H₃₃ClFeN₃O₂P₂
• 分子量: 637.808
• InChiKey: SBUGXPGUKRLXTK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.31
• 重原子数：
  36
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  105
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  cis-[Fe(N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine)(CO)(Cl)2] 、 一氧化碳 、 silver trifluoromethanesulfonate 以 硝基甲烷 为溶剂， 以60%的产率得到trans-[Fe(NC5H4(NHP(i-Pr)2)2)(CO)2Cl]O3SCF3
  参考文献：
  名称：

  Kinetically Controlled Formation of Octahedral trans-Dicarbonyl Iron(II) PNP Pincer Complexes: The Decisive Role of Spin-State Changes

  摘要：

  Treatment of either cis-[Fe(PNP)(X-2)(CO)], trans-[Fe(PNP)(X-2)(CO)], or [Fe(PNP)X-2] (X = Cl, Br; PNP are tridentate pincer-type ligands based on 2,6-diaminopyridine and 2,6-diaminopyrimidine) with I equiv of AgBF4 in the presence of CO afforded selectively octahedral iron(I complexes of the type trans-[Fe(PNP)(CO)(2)X](+). The same reaction carried out with irons-trans-[Fe-PNP-iPr)(Cl)(2)(CO)] in the absence of CO affords also trans-[Fe-Te(PNP-/Pr)(CO)(2)Cl](+) together with unidentified paramagnetic species. This reaction involves an intermolecular CO transfer between coordinately unsaturated [Fe(PNP-iPr)(CO)(Cl)](+) intermediates. In all reactions studied, there was no evidence for the formation of cis dicarbonyl complexes. X-ray structures of representative complexes are presented. A detailed mechanism, based on DFT/B3LYP calculations, is presented, suggesting that upon irreversible removal of X transient cationic intermediates [Fe(PNP)(CO)(X)](+) of two conformations, one with the CO in the apical and the halide in the basal position (A) and vice versa (B), are formed. These adopt a singlet ground state in the case of A and a triplet ground state in the case of B. The formation of trans-[Fe(PNI)(CO)(2)X](+) is kinetically controlled, with A in the singlet ground state being the key intermediate. Pathways originating from complexes with a triplet ground state are "spin-blocked" (spin forbidden) or thermodynamically disfavored.

  DOI：

  10.1021/om1001638

文献信息

• Unusual Anion Effects in the Iron‐Catalyzed Formation of 3‐Hydroxyacrylates from Aromatic Aldehydes and Ethyl Diazoacetate
  作者：Luis Gonçalo Alves、Georg Dazinger、Luis F. Veiros、Karl Kirchner

  DOI：10.1002/ejic.201000240

  日期：2010.7

  Due to the lability of one of the CO ligands in trans-[Fe(PNP)-(CO) 2 CI] + this compound is an efficient catalyst for the coupling of a series of aromatic aldehydes with ethyl diazoacetate (EDA), which give, in most cases, selectively 3-hydroxyacrylates rather than β-oxo esters. This reaction is strongly dependent on the nature of the counterion. Whereas with BF 4 - the reaction proceeds with conversions

  由于反式-[Fe(PNP)-(CO) 2 CI] + 中的一个 CO 配体的不稳定性，该化合物是一系列芳香醛与重氮乙酸乙酯 (EDA) 偶联的有效催化剂，可生成在大多数情况下，选择性地使用 3-羟基丙烯酸酯而不是 β-氧代酯。该反应强烈依赖于反离子的性质。而对于 BF 4 - 反应以高达 90% 的转化率进行，对于反离子 NO 3 - 、CF 3 COO - 、CF 3 SO 3 - 、SbF 6 - 和 BAr' 4 - [Ar' = 3 ,5-(CF 3 ) 2 C 6 H 3 ]没有反应发生。在 PF 6 的情况下，仅实现了高达 20% 的转化率。通过 DFT/B3LYP 计算建立了芳香醛与 EDA 偶联的可能机制，这使得化学选择性和抗衡离子的作用合理化。