[(1',2,2',3,3',4,4',5-octamethylferrocenyl)methyl]triphenylphosphonium bromide | 877307-33-0

• 英文名称: [(1',2,2',3,3',4,4',5-octamethylferrocenyl)methyl]triphenylphosphonium bromide
• 英文别名: [(2,2',3,3',4,4',5,5'-octamethylferrocenyl)methyl]triphenylphosphonium bromide；((1',2,2'3,3',4,4',5-octamethylferrocenyl)methyl)triphenylphosphonium bromide；(1',2,2',3,3',4,4',5-octamethylferrocenyl)methyltriphenylphosphonium bromide；1',2,2',3,3',4,4',5-octamethylferrocenylmethylphosphoniumbromide
• CAS: 877307-33-0；185543-98-0
• 化学式: Br*C₃₇H₄₂FeP
• 分子量: 653.465
• InChiKey: LASWMIMSYCMWHH-UHFFFAOYSA-M

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：

  5-硝基噻吩-2-甲醛 、 [(1',2,2',3,3',4,4',5-octamethylferrocenyl)methyl]triphenylphosphonium bromide 在 potassium tert-butoxide 作用下， 以 四氢呋喃 为溶剂， 以72%的产率得到
  参考文献：
  名称：

  基于八甲基二茂铁供体单元的氧化还原互变的 NLO 活性供体-受体分子的第一超极化率的可逆转换

  摘要：

  化合物 1 含有通过乙烯基接头与硝基噻吩受体连接的八甲基二茂铁供体，其静态第一超极化率 β0 为 95(±10) × 10-30 esu，在八甲基二茂铁单元的氧化；这为化合物的 NLO 特性提供了简单的基于氧化还原的转换。

  DOI：

  10.1039/b008056j
• 作为产物：
  描述：

  1-(hydroxymethyl)-1',2,2',3,3',4,4',5-octamethylferrocene 、 三苯基膦氢溴酸盐 以 甲苯 为溶剂， 以97%的产率得到[(1',2,2',3,3',4,4',5-octamethylferrocenyl)methyl]triphenylphosphonium bromide
  参考文献：
  名称：

  在光合作用模型中二茂铁官能化的Zn-咪唑基-卟啉作为潜在的末端电子供体的滑面卟啉二聚体的合成及其电化学性质

  摘要：

  系统的系列 二茂铁合成功能化的Zn-咪唑基-卟啉以组装成滑面 卟啉二聚体通过咪唑基与锌的互补配位作为人工光合作用模型。在卟啉环的内消旋位置上用二茂铁和八甲基二茂铁直接取代会产生特征性的电子结构，而通过亚苯基-亚乙烯基和亚苯基-乙烯间隔基的二茂铁取代基会减轻电子通讯。通过末端的给电子能力的程度使Q带的红移，卟啉环的荧光猝灭和氧化还原电势合理化二茂铁。

  DOI：

  10.1039/b506992k

文献信息

• New Soluble Bis[nona-, octa-, and pentamethylferrocenes] as “Molecular Wires” with a Metal-to-Metal Distance of up to 40 Å
  作者：Andreas Hradsky、Benno Bildstein、Norbert Schuler、Herwig Schottenberger、Peter Jaitner、Karl-Hans Ongania、Klaus Wurst、Jean-Pierre Launay

  DOI：10.1021/om960676w

  日期：1997.2.1

  Methylated ferrocenes are useful building blocks for novel materials in molecular electronics with advantageous properties in comparison to normal ferrocene derivatives. The presence of nine, eight, or five methyl substituents leads to (i) a decrease in oxidation potential, (ii) amplified donor capacity with correspondingly increased stability of the ferrocenium salts, and, most significantly, (iii)

  甲基化的二茂铁是分子电子学中新型材料的有用组成部分，与常规的二茂铁衍生物相比，具有优越的性能。九个，八个或五个甲基取代基的存在导致（i）氧化电位降低，（ii）增强的供体容量以及相应的二茂铁鎓盐稳定性增加，最重要的是（iii）溶解度增加。基于标准维蒂希化学方法的模块化合成方法提供了由多达五个亚乙烯基-亚苯基亚单元桥接的π-共轭可溶的壬二，八-和五甲基化的二茂铁。这些带有间隔基的双二茂铁是“分子线”，金属与金属之间的距离最高达40Å，有效的共轭路径最高达50Å。
• Synthesis and electrochemistry of novel heteronuclear Fe–Ru bi- and quatermetallocenes, conjugatively connected by ethene and thiophene bridges
  作者：Dagmar Obendorf、Herwig Schottenberger、Klaus Wurst、Norbert Schuler、Gerhard Laus

  DOI：10.1016/j.jorganchem.2004.09.087

  日期：2005.1

  (E)-2-(1'-Formylruthenocenyl)ethenyl-1',2,2',3,3',4,4',5-octamethylferrocene (1) and (all-E)-2,5-bis[2-[1'-[2-(1',2,2',3,3',4,4',5-octamethylferrocenyl)ethenyl]ruthenocenyl]ethenyl]thiophene (2) were synthesized by a sequence of Wittig olefinations. The X-ray structure of 1 is reported. The cyclic voltammogram of compound 1 shows the irreversible one-electron transfer expected for ruthenocene and a reversible wave for the octamethylferrocene moiety. Both waves occur at about the same potential as observed for the parent metallocenes. Compound 2, however, exhibits completely unusual redox properties. In contrast to most ruthenocene-containing compounds, a reversible two-electron transfer is observed at a significantly lower potential than found usually for ruthenocenes that can be attributed unambiguously to the independent oxidation/reduction of the two ruthenocene moieties. The unexpected stability of the oxidation products must be due to the presence of the thiophene-ethene bridge, which facilitates the oxidation reaction and stabilizes the reaction products by delocalization of the valence electrons. (C) 2004 Elsevier B.V. All rights reserved.

  (E)-2-(1'-形甲醛 Ruthenocenyl) vinyl-1',2,2',3,3',4,4',5-八甲基铁 Suzuki (1) 和 (全部 E)-2,5-双[2-[1'-[2-(1',2,2',3,3',4,4',5-八甲基铁 Suzuki) vinyl]Ruthenocenyl] vinyl] thiophene (2) 通过 Wittig羰化反应依次合成为两个 ruthenocene 合成物。 Ruthenocene 合成物 1 的 X 射线结构简式报告了。化合物 1 的循环伏安图显示预期的不可逆单电子转移和八甲基铁 Suzuki 块的可逆波。与 ruthenocene 的其他同系物显示出接近相同的电位。相比之下，化合物 2 呈现出完全不同的氧化还原行为。与大多数 ruthenocene 合成物不同，在一个显著较低的电位附近实现了可逆的两电子转移。 这种意外的氧化物的稳定性可能是由于带有 thiophene-乙二烯桥的存在，这极大地促进了氧化反应并通过价电子的相互作用稳定了反应产物。 (C) 2004 伊出书出版公司 All 右边受保留。
• Effects of metal atom motion and ring rotation in iron organometallics. Synthesis of isotopically labelled nonamethyl [57Fe]ferrocene
  作者：Rolfe H. Herber、Israel Nowik、Herwig Schottenberger、Klaus Wurst、Norbert Schuler、Adrian Gallus Mueller

  DOI：10.1016/s0022-328x(03)00778-2

  日期：2003.10

  Temperature dependent Fe-57 Mossbauer effect studies on nonamethyl ferrocene (NMF), have been carried out on isotopically enriched material over the temperature range 90 < T < 290 K. These measurements have led to the elucidation of the dynamical behaviour of the iron atom and reflect the onset of ring rotation and libration. These results are compared to corresponding data for ferrocene and related compounds. A convenient small scale synthesis suited for the preparation of Fe-57-enriched nonamethylferrocene which allows its easy separation in pure form, is also presented. With the exception of nonamethylferrocene, which is unresolvable due to its lattice-neighbour related conformational ring disorders, X-ray structure determinations of all new compounds of the reaction sequence, and of the starting compound hydroxymethyloctamethylferrocene (octamethylferrocenyl methanol) have been performed. (C) 2003 Elsevier B.V. All rights reserved.
• Ferrocenyl-Terminated Redox Stars: Synthesis and Electrostatic Effects in Mixed-Valence Stabilization
  作者：Abdou K. Diallo、Christelle Absalon、Jaime Ruiz、Didier Astruc

  DOI：10.1021/ja109380u

  日期：2011.1.26

  A family of rigid ferrocenyl-terminated redox stars has been synthesized-by Negishi coupling, including hexa(ferrocenethynyl)benzene complexes, a dodecaferrocenyl star, and stars with extended rigid tethers and fully characterized. Cyclic voltammetry (CV) studies of the parent complex hexa(ferrocenyl-ethynyl)benzene, 1, show a single wave for the six-electron oxidation of 1 using Nn-Bu4PF6 as the supporting electrolyte on a Pt anode in CH2Cl2, whereas three distinct two-electron reversible CV waves are observed using Nn-Bu4BAr4F (Ar-F = 3,5-C6H3-(CF3)(2)). The CV of 1,3,5-tris(ferrocenylethynyl)benzene, 11, also shows only one wave for the three-electron transfer with Nn-Bu4PF6 and three one-electron waves using Nn-Bu4BAr4F. This confirms the lack of electronic communication between the ferrocenyl groups and a significant electrostatic effect among the oxidized ferrocenyl groups. This effect is not significant between para-ferrocenyl groups in 1,4-bis(ferrocenylethynyl)benzene for which only a single wave is observed even with Nn-Bu4BAr4F as the supporting electrolyte. The para-ferrocenyl substituents are quite independent, which explains that two para-ferrocenyl groups are oxidized at about the same potential in a single CV wave of 1. With the additional steric bulk introduced with a methyl substituent on the ferrocenyl group, however, even the para-methylferrocenyl groups are submitted to a small electrostatic effect splitting the six-electron transfer into six single-electron waves, probably because of the overall steroelectronic constraints. Contrary to 11, 1,3-bis(ferrocenylethynyl)benzene and related complexes with a third, different substituent in the remaining meta position different from a ferrocenylethynyl only show a single two-electron wave using Nn-Bu4BAr4F, which is attributed to the transoid conformation of the ferricinium groups minimizing the electrostatic effect. This shows that, in 11, it is the steric frustration that is responsible for the electrostatic effect, and the same occurs in 1. In several cases, Delta E-p is much larger than the expected 60 mV value, characterizing a quasi-reversible (i.e., relatively slow) redox process. It is suggested that this slower electron transfer be attributed to conformational rearrangement of the ferrocenyl groups toward the transoid position in the course of electron transfer. Thus both the thermodynamic and kinetic aspects of the electrostatic factor (isolated from the electronic factor), including the frustration effect, are characterized. The distinction between the electronic communication and through-space electrostatic effect was made possible in all of these complexes in which the absence of wave splitting using a strongly ion-pairing electrolyte shows the absence of significant electronic communication, and was confirmed by the new frustration phenomenon.
• Malaun, Michael; Kowallick, Ralph; McDonagh, Andrew M., Journal of the Chemical Society. Dalton Transactions (2001), 2001, # 20, p. 3025 - 3038
  作者：Malaun, Michael、Kowallick, Ralph、McDonagh, Andrew M.、Marcaccio, Massimo、Paul, Rowena L.、Asselberghs, Inge、Clays, Koen、Persoons, Andre、Bildstein, Benno、Fiorini, Celine、Nunzi, Jean-Michel、Ward, Michael D.、McCleverty, Jon A.

  DOI：——

  日期：——