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首页> 外文学位 >Electrochemistry of transition metal halide and oxide halide complexes in room temperature haloaluminate ionic liquids.
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Electrochemistry of transition metal halide and oxide halide complexes in room temperature haloaluminate ionic liquids.

机译：室温卤铝酸盐离子液体中过渡金属卤化物和氧化物卤化物配合物的电化学。

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摘要

The electrochemistry and absorption spectroscopy of the anionic iridium, niobium, and osmium chloride complexes and the niobium oxide chloride complexes were investigated in the basic composition region of the room temperature haloaluminate ionic liquid, aluminum chloride-1-methyl-3-ethylimidazolium chloride (AlCl{dollar}sb3{dollar}-MeEtimCl). The bromide complexes of iron and titanium were subjected to similar studies in the related aluminum bromide-1-methyl-3-ethylimidazolium bromide (AlBr{dollar}sb3{dollar}-MeEtimBr) system. In addition, a procedure for removing oxide impurities from the AlCl{dollar}sb3{dollar}-MeEtimCl molten salt with phosgene was explored.; Both the (IrCl{dollar}sb6{dollar}) {dollar}sp{lcub}2-/3-{rcub}{dollar} and the (OsCl{dollar}sb6{dollar}) {dollar}sp{lcub}2-/3-{rcub}{dollar} redox systems exhibit classical reversible, uncomplicated electrochemical behavior at glassy carbon electrodes in the basic AlCl{dollar}sb3{dollar}-MeEtimCl ionic liquid in contrast to their behavior in aqueous solution. Electronic absorption spectra that were recorded for the (IrCl{dollar}sb6{dollar}) {dollar}sp{lcub}2-{rcub}{dollar}, (IrCl{dollar}sb6{dollar}) {dollar}sp{lcub}3-{rcub}{dollar}, (OsCl{dollar}sb6{dollar}) {dollar}sp{lcub}2-{rcub}{dollar}, and (OsCl{dollar}sb6{dollar}) {dollar}sp{lcub}3-{rcub}{dollar} complexes in this solvent show no evidence of the distortions due to solvation and solvolysis phenomena that are commonly seen in the spectra of these ions in many molecular solvents.; Electronic absorption spectroscopy indicated that niobium(V) is complexed as (NbCl{dollar}sb6{dollar}) {dollar}sp-{dollar} in basic AlCl{dollar}sb3{dollar}-MeEtimCl. This species can be reduced to (NbCl{dollar}sb6{dollar}) {dollar}sp{lcub}2-{rcub}{dollar} and (NbCl{dollar}sb6{dollar}) {dollar}sp{lcub}3-{rcub}{dollar} in two successive, one-electron, reversible electrode reactions. It is possible to prepare stable solutions of the latter species by using controlled potential electrolysis. The addition of oxide in the form of Li{dollar}sb2{dollar}CO{dollar}sb3{dollar} to solutions of (NbCl{dollar}sb6{dollar}) {dollar}sp-{dollar} produces (NbOCl{dollar}sb5{dollar}) {dollar}sp{lcub}2-{rcub}{dollar}, which can be electrochemically reduced to a magenta colored niobium(IV) complex, possibly (NbOCl{dollar}sb4{dollar}) {dollar}sp{lcub}2-{rcub}{dollar}. The Nb(V)/Nb(IV) oxide chloride electrode reaction exhibits quasireversible behavior.; Iron(III) and titanium(IV) appear to be complexed as (FeBr{dollar}sb4{dollar}) {dollar}sp-{dollar} and (TiBr{dollar}sb6{dollar}) {dollar}sp{lcub}2-{rcub}{dollar}, respectively, in basic AlBr{dollar}sb3{dollar}-MeEtimBr. Both species undergo one-electron, reversible electrode reactions in this solvent similar to those observed for their chloride analogs in AlCl{dollar}sb3{dollar}-MeEtimCl.; Stokes-Einstein products were estimated for each of the complexes examined in this study. The relative radii of the diffusing species, which were estimated from these products, were found to be strongly dependent upon the overall charge of each complex ion and were relatively independent of the oxidation state of the metal core or the coordination geometry of the complex. (Abstract shortened with permission of author.)
机译：在室温卤代铝酸盐离子液体氯化铝-1-甲基-3-乙基咪唑鎓氯化铝（AlCl）的基本组成区域内研究了阴离子铱，铌和氯化and配合物以及氯化铌氯化物的电化学和吸收光谱{dollar} sb3 {dollar} -MeEtimCl）。铁和钛的溴化物络合物在相关的溴化铝-1-甲基-3-乙基咪唑鎓溴化物（AlBr {dollar} sb3 {dollar} -MeEtimBr）系统中进行了相似的研究。另外，探索了用光气从AlCl {sb3 {sb3 {dollar} -MeEtimCl}熔融盐中去除氧化物杂质的方法。 （IrCl {dollar} sb6 {dollar}）{dollar} sp {lcub} 2- / 3- {rcub} {dollar}和（OsCl {dollar} sb6 {dollar}）{dollar} sp {lcub} 2 -/ 3- {rcub} {dollar}氧化还原体系与碱性水溶液相比，在碱性AlCl {sb3 {dollar} -MeEtimCl离子液体中的玻璃碳电极上表现出经典的可逆，简单的电化学行为。为（IrCl {dollar} sb6 {dollar}）{dollar} sp {lcub} 2- {rcub} {dollar，（IrCl {dollar} sb6 {dollar}）{dollar} sp {lcub } 3- {rcub} {dollar}，（OsCl {dollar} sb6 {dollar}）{dollar} sp {lcub} 2- {rcub} {dollar}和（OsCl {dollar} sb6 {dollar}）{dollar}该溶剂中的sp {lcub} 3- {rcub} {dollar}络合物没有显示出由于溶剂化和溶剂分解现象而引起的畸变的迹象，而这种现象通常在许多分子溶剂中这些离子的光谱中可见。电子吸收光谱法表明，铌（V）在碱性AlCl {dol} sb3 {dollar} -MeEtimCl中复合为（NbCl {sb6 {dollar}）{dollar} sp- {dollar}。该物种可减少为（NbCl {dollar} sb6 {dollar}）{dol} sp {lcub} 2- {rcub} {dollar}和（NbCl {dollar} sb6 {dollar}）{dollar} sp {lcub} 3 -{rcub} {dollar}在两个连续的单电子可逆电极反应中。通过使用受控电位电解可以制备后一种物质的稳定溶液。在（NbCl {dollar} sb6 {dollar}）{dollar} sp- {dollar}的溶液中添加Li {dollar} sb2 {dollar} CO {dollar} sb3 {dollar形式的氧化物会产生（NbOCl {dollar } sb5 {dollar}）{dol} sp {lcub} 2- {rcub} {dollar}，可以电化学还原成品红色的铌（IV）络合物，可能是（NbOCl {dollar} sb4 {dollar}）{dollar } sp {lcub} 2- {rcub} {dollar}。 Nb（V）/ Nb（IV）氧化物氯化物电极反应表现出准可逆行为。铁（III）和钛（IV）似乎复合为（FeBr {dollar} sb4 {dollar}）{dol} sp- {dollar}和（TiBr {dollar} sb6 {dollar}）{dollar} sp {lcub}基本AlBr {dollar} sb3 {dollar} -MeEtimBr中的2- {rcub} {dollar}。两种物质都在该溶剂中进行单电子可逆电极反应，类似于在AlCl {sb3 {sdol3}}中的氯化物类似物所观察到的反应。对于本研究中检查的每种复合物，都估算了Stokes-Einstein产品。由这些产物估计的扩散物质的相对半径被发现强烈地取决于每个络合物离子的总电荷，并且相对独立于金属核的氧化态或络合物的配位几何形状。 （摘要经作者许可缩短。）

著录项

  • 作者

    Sun, I-Wen.;

  • 作者单位

    The University of Mississippi.;

  • 授予单位 The University of Mississippi.;
  • 学科 Chemistry Analytical.; Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 1989
  • 页码 151 p.
  • 总页数 151
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;无机化学;
  • 关键词

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