trans-[iron(II) hydride (η2-dihydrogen)bis[1,2-bis(diphenylphosphanyl)ethane]] tetrafluoroborate | 109750-49-4

• 英文名称: trans-[iron(II) hydride (η2-dihydrogen)bis[1,2-bis(diphenylphosphanyl)ethane]] tetrafluoroborate
• 英文别名: trans-[FeH(H2)(1,2-bis(diphenylphosphino)ethane)2]BF4；trans{Fe(η2-H2)(H)(dppe)2}BF4；trans-[(1,2-bis(diphenylphosphino)ethane)2Fe(H)(η2-H2)][BF4]；trans-[FeH(H2)(Ph2PCH2CH2PPh2)2](BF4)；trans-[FeH(η2-H2)(dppe)2]BF4；{Fe(.eta2-H2)(H)(PPh2CH2CH2PPh2)2}BF4
• CAS: 109750-49-4
• 化学式: BF₄*C₅₂H₅₁FeP₄
• 分子量: 942.524
• InChiKey: OCWUEAMEQFDXCE-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：

  trans-[iron(II) hydride (η2-dihydrogen)bis[1,2-bis(diphenylphosphanyl)ethane]] tetrafluoroborate 在 triethylamine 作用下， 以 丙酮 为溶剂， 生成 {Fe(H)2(dppe)2}
  参考文献：
  名称：

  阴离子对阳离子二氢络合物反式-[FeH(η2-H2)(dppe)2]+去质子化的关键作用

  摘要：

  二氢配合物反式-[FeH(eta2-H2)(dppe)2]+ 与过量的 NEt3 形成顺式-[FeH2(dppe)2] 的反应动力学显示出与金属络合物和碱。当溶剂从 THF 变为丙酮时，相应的二级速率常数仅显示微小变化。然而，含有 BF4-、PF6- 和 BPh4- 阴离子的盐的存在会引起更大的动力学变化，BF4- 和 PF6- 会加速反应，而在 BPh4- 存在时反应会减速。考虑到由络合物和阴离子形成的离子对提供比通过未配对金属络合物更有效的反应途径，可以解释这些结果。从丙酮溶液中的动力学结果，已经推导出离子对的稳定性和它们转化为反应产物的速率常数。理论计算提供了关于阴离子不存在和存在时反应机制的额外信息。在所有情况下，反应发生时质子从反式二氢化物通过中间结构转移到碱，显示 Fe-H2...N 和 Fe-H...H...N 二氢键，异构化为顺式产物一旦质子转移步骤完成。离子对的优化几何结构表明阴离子靠近

  DOI：

  10.1021/ja070939l
• 作为产物：
  描述：

  四氟硼酸-二乙醚络合物 、 cis-{Fe(H)2(dppe)2} * 2C7H8 以 四氢呋喃 为溶剂， 以80%的产率得到trans-[iron(II) hydride (η2-dihydrogen)bis[1,2-bis(diphenylphosphanyl)ethane]] tetrafluoroborate
  参考文献：
  名称：

  .eta.2-二氢过渡金属配合物的单晶 X 射线和中子衍射研究：trans-[Fe(.eta.2-H2)(H)(PPh2CH2CH2PPh2)2]BPh4

  摘要：

  {eta}{sup 2}H{sub 2} 配体中的 HH 距离 (Fe({eta}{sup 2}-H{sub 2})H(dppe){sub 2})BPh{sub 4} , 1 BPh{sub 4}, dppe = PPh{sub 2}CH{sub 2}CH{sub 2}PPh{sub 2}，由体积为 2.62 的晶体上的中子衍射确定为 0.816 (16) {埃} mm{sup 3} at 20 K: 1-BPh{sub 4} 是单斜晶系，空间群 C2/c, a = 16.999 (7) {埃}, b = 16.171 (2) {埃}, c = 22.114 (5 ) {埃}, {beta} = 102.52 (2){degree}, U = 5,934.4 (2) {埃} {sup 3}，和 D{sub c} = 1.315 g cm{sup {minus}3} Z = 4; R(F) =

  DOI：

  10.1021/ja00206a009

文献信息

• Synthesis and Characterization of the First Examples of Dicationic Dihydrogen Complexes of Iron and Ruthenium with the PF ₃ Ligand
  作者：H. V. Nanishankar、Munirathinam Nethaji、Balaji R. Jagirdar

  DOI：10.1002/ejic.200400130

  日期：2004.8

  dihydrogen complexes of the type trans- $[M(\eta ^2-H_2)(PF_3)(diphosphane)_2]^2+ [M = Ru, diphosphane = dppm (Ph_2PCH_2PPh_2); M = Fe, Ru, diphosphane = dppe (Ph_2PCH_2CH_2PPh_2)]$ have been prepared from the precursor hydrides trans- $[M(H)(PF_3)(diphosphane)_2]^+ $ upon reaction with HOTf. In the case of dppm, in addition to the trans-dihydrogen complex ci \varsigma-$[Ru(\eta^2-H_2)(PF_3)(dppm)_2]^2+ $was

  反式-$[M(\eta^2-H_2)(PF_3)(diphosphane)_2]^2+ [M = Ru, diphosphane = dppm (Ph_2PCH_2PPh_2); M = Fe, Ru, diphosphane = dppe (Ph_2PCH_2CH_2PPh_2)]$ 已从前体氢化物反式 $[M(H)(PF_3)(diphosphane)_2]^+$ 与 HOTf 反应制备。在dppm的情况下，质子化反应中除了得到反式二氢络合物ci\varsigma-$[Ru(\eta^2-H_2)(PF_3)(dppm)_2]^2+$。这些衍生物中 HH 键的完整性质已使用自旋晶格弛豫时间测量（短 T_1$ 值）和 HD 同位素异构体的大 $J_H_,_D$ 耦合常数确定。HH 键长和二氢配合物的稳定性根据 $PF_3$ 配体的酸度进行讨论，并与其他具有反式 CO 和 CNH 配体的系统进行比较。发现
• 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。
• Bautista, Maria T.; Cappellani, E. Paul; Drouin, Samantha D., Journal of the American Chemical Society, 1991, vol. 113, # 13, p. 4876 - 4887
  作者：Bautista, Maria T.、Cappellani, E. Paul、Drouin, Samantha D.、Morris, Robert H.、Schweitzer, Caroline T.、Sella, Andrea、Zubkowski, Jeffery

  DOI：——

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

  DOI：——

  日期：——
• Effect of the Ligand and Metal on the pKa Values of the Dihydrogen Ligand in the Series of Complexes [M(H2)H(L)2]+, M = Fe, Ru, Os, Containing Isosteric Ditertiaryphosphine Ligands, L
  作者：E. Paul Cappellani、Samantha D. Drouin、Guochen Jia、Patricia A. Maltby、Robert H. Morris、Caroline T. Schweitzer

  DOI：10.1021/ja00087a024

  日期：1994.4

  The new dihydrogen complexes trans-[MH(H-2)L(2)]BF4, L = P(C6H4-4-R)(2)CH2CH2P(C6H4-4-R)(2), R = CF3, M = Fe, Ru, and Os, R = CH3, M = Fe, R = OMe, M = Ru, are prepared by reaction of the dihydride complexes MH(2)L(2) With HBF4. The H-H bond length of the spinning H-2 ligand does not change significantly as a function of R (from CF3 to CH3 when M = Fe and from CF3 to OCH3 for M = Ru) according to H-1 NMR T-1 and (1)J(HD) measurements while there is a lengthening for the Os complexes. The rate constants for H atom exchange (reflecting the ease of homolytic splitting of H-2) increase with the increasing donor ability of R for a given metal as do the pK(a) values (reflecting a decrease in ease of heterolytic splitting). The electrochemical properties of some complexes MH(Cl)L(2) and MH(2)L(2) are reported. As expected H-2 acidity decreases as the parent hydride becomes easier to oxidize with this change in R (same M). The trend in dihydrogen pK(a) values as a function of the metal, Fe < Os < Ru, is distinctively different to the trend in pK(a) values of the dihydride complexes M(H)(2)(CO)(4), Fe < Ru < Os, and [M(C5H5)(H)(2)(PPh(3))(2)](+), Ru < Os, The high H-H bond energy of the RU(2+) complexes trans-[RuH(H-2)L(2)]BF4 is probably the reason why they are less acidic than corresponding Os2+ complexes. A consideration of the pK(a) values correctly indicated that a RuH(2)L(2)/[RuH(H-2)L(2)](+) mixture would be more effective at H/D exchange between D-2 and HO(t)Bu than the dihydrogen complex alone.