trans-[FeH(acetonitrile)(dppe)2][BF4] | 252659-25-9

• 英文名称: trans-[FeH(acetonitrile)(dppe)2][BF4]
• 英文别名: trans-[(1,2-bis(diphenylphosphino)ethane)2Fe(H)(CH3CN)][BF4]
• CAS: 252659-25-9
• 化学式: BF₄*C₅₄H₅₂FeNP₄
• 分子量: 981.56
• InChiKey: ZPLIZEWQCPLWTG-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

• 作为反应物：
  描述：

  potassium cyanide 、 trans-[FeH(acetonitrile)(dppe)2][BF4] 以 四氢呋喃 、 甲醇 为溶剂， 以75%的产率得到trans-[FeH(CN)(PPh2(CH2)2PPh2)2]
  参考文献：
  名称：

  Iron(II)–nitrile complexes: synthesis, structure and property of trans-[FeH(NCR)(dppe)2]+X− (dppe=Ph2PCH2CH2PPh2: R=CH3, CH2CH2OCH3, CH2CH2CH2Cl, C6H5: X=Cl, BPh4, BF4)

  摘要：

  Dissolution of trans-FeHCl(dppe)(2), 1, in various nitriles under argon led to the formation of complexes of the type trans-[FeH(NCR)(dppe)(2)]Cl (2a (R = CH3), 3a (R = CH2CH2OMe), 4a (R = CH2CH2CH2Cl), 5a (R = Ph)) in several hours. Complexes 2a-4a could be further converted to trans-[FeH(NCR)(dppe)(2)][BPh4] (2b-4b) and trans-[FeH(NCR)(dppe)(2)[BF4] (2c-4c) when they were treated with NaBPh4 and NaBF4, respectively, The stability and electrochemical properties of these complexes appeared to depend mainly on their counteranions (Cl-, BPh4-, BF4-). Compounds 2b, 2c, 3b, 3c, 4b and 4c reacted with KCN or NaCN to give [FeH(CN)(dppe)(2)] (6). Compound 6 underwent electrophilic addition at the cyano nitrogen by RSO3CF3 (R = Me, H) to give FeH(CNR)(dppe)(2)][SO3CF3] (7a for R = Me, 7b for R = H). Crystallographic data for 2b: monoclinic space group P2(1)/c, a = 22.508(1) Angstrom, b = 16.120(1) Angstrom, c = 19.257(1) Angstrom, beta = 113.86(1)degrees, Z = 4, R(wR(2)) = 0.0361(0.0882). Crystallographic data for 3b: triclinic space group P (1) over bar, a = 13.240(1) Angstrom, b = 14.732(2) Angstrom, c = 19.807(1) Angstrom, alpha = 75.276(6)degrees, beta = 72.466(6)degrees, gamma = 82.033(6)degrees, Z = 2, R(wR(2)) = 0.0368(0.0835). Crystallographic data for 7a: monoclinic space group PZ,lc, a = 12.456(1) Angstrom, b = 21.880(3) Angstrom, c = 19.924(3) Angstrom, beta = 108.08(1)degrees, Z = 4, R(wR(2)) = 0.0663 (0.1647). (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00392-7
• 作为产物：
  描述：

  trans-[(1,2-bis(diphenylphosphino)ethane)2Fe(η2-H2)(CH3CN)][BF4]2 在 triethylamine or pyridine or piperidine 作用下， 以 氘代氯仿 为溶剂， 生成 trans-[FeH(acetonitrile)(dppe)2][BF4]
  参考文献：
  名称：

  Nanishankar; Nethaji, Munirathinam; Jagirdar, Balaji R., Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 2003, vol. 42, # 9, p. 2332 - 2338

  摘要：

  DOI：

文献信息

• Solvent and incoming ligand effects on the mechanism of substitution reactions of trans-[FeH(L)(DPPE)2]+ (L = MeCN), and comparison with the dihydrogen analogue (L = H2) †
  作者：Manuel G. Basallote、Joaquín Durán、María J. Fernández-Trujillo、Gabriel González、M. Angeles Máñez、Manuel Martínez

  DOI：10.1039/a905377h

  日期：——

  Reaction of trans-[FeH(MeCN)(DPPE)2]+ with PhCN to form trans-[FeH(PhCN)(DPPE)2]+ occurred with a single measurable kinetic step in THF, acetone or MeOH solutions (DPPE = Ph2PCH2CH2PPh2). The observed rate constants are independent of the concentration of the nucleophile and do not change very much with the solvent nature. However, the activation parameters are strongly solvent-dependent, especially ΔV ‡ that changes from 20 cm3 mol–1 in THF to 35 cm3 mol–1 in neat benzonitrile. Kinetic results for the reactions of trans-[FeH(MeCN)(DPPE)2]+ with substituted benzonitriles indicate that kinetic parameters for the substitution of co-ordinated MeCN also change with the nature of the entering ligand. The reactions of trans-[FeH(L)(DPPE)2]+ complexes (L = MeCN or H2) with the bidentate ligands C6H4(CN)2 (1,2-dicyanobenzene) and Me2PCH2CH2PMe2 (DMPE) have been also monitored by NMR at variable temperature. While for the acetonitrile complex and dicyanobenzene, trans-[FeHC6H4(CN)2}(DPPE)2]+ is the only product detected with no evidence of the formation of reaction intermediates or side-products, small amounts of free DPPE are detected for the same reaction with the dihydrogen complex to form the same monosubstituted complex. Moreover, whereas the acetonitrile complex does not react with DMPE, free DPPE is the only DPPE-containing product after reaction of trans-[FeH(H2)(DPPE)2]+ with DMPE excess. The whole of the kinetic data and NMR observations are, on the one hand, consistent with a chelate ring-opening mechanism for the reactions of the dihydrogen complex and, on the other hand with a simple dissociative mechanism for the reactions of the acetonitrile complex. In all cases, the absolute values of ΔV ‡ for these reactions are larger than usual and also show an unusual dependence on the nature of the solvent and the entering ligand.

  反式-[FeH(MeCN)(DPPE)2]+与 PhCN 反应生成反式-[FeH(PhCN)(DPPE)2]+，在 THF、丙酮或 MeOH 溶液（DPPEÂ =Â Ph2PCH2CH2PPh2）中只需一个可测量的动力学步骤。观察到的速率常数与亲核体的浓度无关，也不随溶剂性质发生很大变化。然而，活化参数与溶剂密切相关，尤其是δVâ¡，从四氢呋喃中的 20 cm3 molâ1 变为纯苯腈中的 35 cm3 molâ1。反式-[FeH(MeCN)(DPPE)2]+ 与取代的苯甲腈反应的动力学结果表明，取代配位的 MeCN 的动力学参数也会随着进入配体的性质发生变化。反式-[FeH(L)(DPPE)2]+ 复合物（LÂ = MeCN 或 H2）与双叉配体 C6H4(CN)2（1,2-二氰基苯）和 Me2PCH2CH2PMe2（DMPE）的反应也在变温条件下通过核磁共振进行了监测。就乙腈络合物和二氰基苯而言，反式-[FeH (CN)2}(DPPE)2]+ 是唯一检测到的产物，没有证据表明形成了反应中间体或副产物，而在与二氢络合物进行相同反应以形成相同的单取代络合物时，则检测到少量游离 DPPE。此外，反式-[FeH(H2)(DPPE)2]+ 与过量 DMPE 反应后，乙腈络合物不会与 DMPE 发生反应，而游离 DPPE 是唯一含有 DPPE 的产物。整个动力学数据和核磁共振观察结果一方面与二氢络合物反应的螯合开环机理相一致，另一方面与乙腈络合物反应的简单离解机理相一致。在所有情况下，这些反应的 ÎV â 的绝对值都比通常的要大，而且还显示出与溶剂和进入配体的性质有关的不寻常的依赖性。