trans-[FeH(CN)(PPh2(CH2)2PPh2)2] | 252659-37-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-[FeH(CN)(PPh2(CH2)2PPh2)2]
• 英文别名: trans-FeH(CN)(dppe)2；trans-[FeH(cyano)(dppe)2]；trans-[FeH(CN)(dppe)2]
• CAS: 252659-37-3；67827-23-0；70428-49-8
• 化学式: C₅₃H₄₉FeNP₄
• 分子量: 879.721
• InChiKey: JKHYFSGKOFZQHJ-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-[FeH(CN)(PPh2(CH2)2PPh2)2] 、 3-溴丙炔 以 further solvent(s) 为溶剂， 以93%的产率得到trans-[Fe(H)(CNCH2C2H)(1,2-bis(diphenylphosphino)ethane)2]Br
  参考文献：
  名称：

  Electrophilic attack of alkyl halide at the cyanide nitrogen in trans-[Fe(H)(CN)(dppe)2]: preparation, structure, and properties of trans-[Fe(H)(CNR)(dppe)2]X (dppe=Ph2PCH2CH2PPh2; R=Me, Et, Pr, i-Pr, n-Bu, CH2CH2Br, CH2CH2CH2I, CH2CHCH2, CH2CCH; X=Br, I)

  摘要：

  Compound trans-[FeH(CN)(dppe)(2)] (1) reacted with alkyl iodides or alkyl bromides to give Fe(II)-organic isocyanide complexes of the type trans-[FeH(CNR)(dppe)(2)]X[X = I: R = Me (2), Et (3), Pr (4), CH2CH2CH2I (5), i-Pr (6), CH2CH=CH2 (7); X = Br: R = Et (8), Pr (9), n-Bu (10), CH2CH2Br (11), CH2CH=CH2 (12), CH2C double bond CH (13)]. Compound 1 reacted with BF3 to give a Lewis acid-base adduct, trans-[FeH(CN -->BF3)(dppe)(2)]. Compounds 5 and 13 were characterized structurally by X-ray diffraction, in which the hydride ligand appears to be involved in the dihydrogen bonding, M-H . . .H-C. (C) 2000 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(00)00252-8
• 作为产物：
  描述：

  potassium cyanide 、 trans-[FeH(3-methoxypropionitrile)(dppe)2][BPh4] 以 四氢呋喃 、 甲醇 为溶剂， 以86%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

文献信息

• Ancillary ligand control of reactivity. Protonation at hydride vs. cyanide in trans-[FeH(CN)(R2PCH2CH2PR2)2](R = Et, Ph, p-tolyl) and X-ray crystal structure determination of trans-[FeH(CNH)(R2PCH2CH2PR2)2]BF4(R =p-tolyl)
  作者：Patrick I. Amrhein、Samantha D. Drouin、Cameron E. Forde、Alan J. Lough、Robert H. Morris

  DOI：10.1039/cc9960001665

  日期：——

  The ancillary ligands in trans-[FeH(CN)L2] control whether protonation occurs at hydride to produce a dihydrogen complex or at cyanide to produce a hydrogen isocyanide complex.

  反式-[FeH(CN)L2] 中的辅助配体可控制质子化是发生在氢化物上以产生二氢络合物，还是发生在氰化物上以产生异氰化氢络合物。
• Synthesis of the acidic dihydrogen complexes trans-[M(H2)(CN)L2]+ and trans-[M(H2)(CNH)L2]2+ where M = Fe, Ru, Os and L = dppm, dppe, dppp, depe, and dihydrogen substitution by the trifluoromethanesulfonate anion to give trans-[Ru(OTf )(CN)L2] or trans-[Ru(OTf )(CNH)L2]OTf †
  作者：Tina P. Fong、Cameron E. Forde、Alan J. Lough、Robert H. Morris、Pierluigi Rigo、Eliana Rocchini、Tim Stephan

  DOI：10.1039/a906717e

  日期：——

  2-bis(diethylphosphino)ethane]) as ancillary ligands influences the stability and the reactivity of these complexes. The iron and osmium complexes are more stable than the ruthenium complexes that lose the dihydrogen ligand and coordinate the trifluoromethanesulfonate anion. The crystal structure of trans-[Ru(OTf)(CN)(dppe)2] is reported. The Ru–OTf bond is weak and so the triflate ligand can be displaced

  非常酸性配合物的反式- [M（η 2 -H 2）（CN）L- 2 ] +和反式- [M（η 2 -H 2）（CNH）L- 2 ] 2+，与配体二氢反式的氰三氟甲磺酸（HOTf ）与Fe（II），Ru（II）和Os（II）。使用不同的金属和膦（dppm = [双（二苯基膦基）甲烷]，dppe = [1,2-双（二苯基膦基）乙烷]，dppp = [1,3-双（二苯基膦基）丙烷]和depe = [1,2-双（二乙基膦基乙烷）乙烷]作为辅助配体影响这些配合物的稳定性和反应性。铁和的络合物比失去二氢配体并配位三氟甲磺酸根阴离子的钌络合物更稳定。报道了反式-[Ru（OTf ）（CN）（dppe）2 ]的晶体结构。在Ru-光学传递函数键是弱等三氟甲磺酸酯配体可以由H移位2（克），得到反式的[Ru（η 2 -H 2）（CN）L- 2] OTf。有稳定的复合物之间的微妙平衡反式- [M（η 2 -H 2）（CN）L-
• 10.1039/b0056871
  作者：Rocchini, Eliana、Rigo, Pierluigi、Mezzetti, Antonio、Stephan, Tim、Morris, Robert H.、Lough, Alan J.、Forde, Cameron E.、Fong, Tina P.、Drouin, Samantha D.

  DOI：10.1039/b0056871

  日期：——
• Cyanide as a versatile Lewis base ligand at a dinitrogen-binding iron(II) centre: mono- and heteronuclear adducts
  作者：Sı́lvia S.P.R Almeida、M.Fátima C Guedes da Silva、Lucjan B Jerzykiewicz、Piotr Sobota、Armando J.L Pombeiro

  DOI：10.1016/s0020-1693(03)00249-4

  日期：2003.12

  The ligated cyanide in trans-[FeH(CN)(dppe)(2)] is activated towards aroylation, alkylation and addition of various transition metal Lewis acids, in particular [WCl4(PPh3)(2)], [ReOCl3(PPh3)(2)], [PdCl2(PPh3)(2)] and [PtCl(Ph)(PPh3)(2)], to give, in the former case, mononuclear isocyanide complexes and, in the latter case, heteronuclear adducts with bridging cyanide. Their syntheses and spectroscopic characterisation are presented, as well as results of the X-ray diffraction analyses of a trinuclear complex with the Fe-Cequivalent toN-W-Nequivalent toC-Fe} unit and of the parent cyano trans-[FeH(CN)(dppe)(2)] complex. The cyanide bridge allows the electronic communication between the metal centres as indicated by a cyclic voltammetric study. (C) 2003 Elsevier Science B.V. All rights reserved.
• Forde, Cameron E.; Landau, Shaun E.; Morris, Robert H., Journal of the Chemical Society, Dalton Transactions, 1997, # 10, p. 1663 - 1664
  作者：Forde, Cameron E.、Landau, Shaun E.、Morris, Robert H.

  DOI：——

  日期：——