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首页> 外文学位 >Synthesis of elaborated imidazoles, and synthesis of PQ models for electron transfer studies.
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Synthesis of elaborated imidazoles, and synthesis of PQ models for electron transfer studies.

机译：合成的咪唑的合成以及用于电子转移研究的PQ模型的合成。

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摘要

The photo-initiated coupling of ({dollar}pi{dollar}-allyl)nickel halide complexes with iodo imidazoles proceeds efficiently in toluene solution without the use of coordinating solvent or added ligand, leading to allylated imidazoles (11 examples, 38-91% yield). Nickel-promoted allylation, and symmetrical coupling, of non-imidazole aryl halides and triflates in toluene solution is enhanced by using N-methylimidazole as an additive. {dollar}sp1{dollar}H NMR analysis of a solution of N-methylimidazole and {dollar}etasp3{dollar}-prenylnickel bromide dimer in C{dollar}sb6{dollar}D{dollar}sb6{dollar} shows coordination of the imidazole N-3 to nickel.; Steady-state fluorescence and transient absorbance measurements have been used to determine electron transfer (ET) rates of four model compounds in which zinc tetratolylporphyrin (P) and naphthoquinone (Q) are held at fixed distances by homologous, fully {dollar}sigma{dollar}-bonded, oligospirocyclic spacers. The synthesis and characterization of the PQ models are described. Structural studies of several spirocyclic systems show that the operative P{dollar}...{dollar}Q separations are {dollar}approx{dollar}5.9, 8.1, 10.2, and 12.1 A, respectively, for the {dollar}sigma{dollar}-pathways containing 6, 8, 10, and 12 bonds. Spectroscopic identification of the P{dollar}sp+{dollar}Q{dollar}sp-{dollar} transient species shows that diminished {dollar}sp1{dollar}P* lifetimes and fluorescence yields result from ET. The ET rates are attenuated per bond according to the relationship k{dollar}sb{lcub}rm ET{rcub}{dollar} = 10{dollar}sp{lcub}12{rcub}{dollar}Aexp(-{dollar}beta{dollar}N{dollar}sbsigma{dollar}), where the values of {dollar}beta{dollar} are 1.03, 1.06, and 1.15 per bond for n-butanol, pyridine, and acetonitrile, respectively.
机译：（{pial} pi {dollar}-烯丙基）卤化镍配合物与碘咪唑的光引发偶合反应在甲苯溶液中高效进行，而无需使用配位溶剂或添加的配体，导致烯丙基化的咪唑（11例，38-91％让）。通过使用N-甲基咪唑作为添加剂，可促进镍在甲苯溶液中的非咪唑基芳基卤化物和三氟甲磺酸酯的烯丙基化和对称偶联。在C {dollar} sb6 {dollar} D {dollar} sb6 {dollar}中N-甲基咪唑和{dol} etasp3 {dollar}-异戊烯基溴化镍二聚体溶液的{dol} sp1 {dollar} H NMR分析咪唑N-3为镍。稳态荧光和瞬态吸光度测量已用于确定四种模型化合物的电子转移（ET）速率，其中四甲苯基卟啉锌（P）和萘醌（Q）通过同源的，完全{dollar} sigma {dollar }键合的螺环间隔基。描述了PQ模型的综合和表征。对几个螺环系统的结构研究表明，对于{sigma} {dollar}，可操作的P {dollar} ... {dollar} Q间隔分别为{dol}大约{dol} 5.9、8.1、10.2和12.1A。 }包含6、8、10和12个键的路径。通过对P {dollar} sp + {dollar} Q {dollar} sp- {dollar}瞬态物种的光谱鉴定，可知ET导致{dollar} sp1 {dollar} P *寿命缩短，荧光产量降低。 ET率根据关系k {dollar} sb {lcub} rm ET {rcub} {dollar} = 10 {dollar} sp {lcub} 12 {rcub} {dollar} Aexp（-{beta} {dollar} N {dollar} sbsigma {dollar}），其中对于正丁醇，吡啶和乙腈，每个键的{dollar} beta {dollar}的值分别为1.03、1.06和1.15。

著录项

  • 作者

    Albaneze, Jennifer Elizabeth.;

  • 作者单位

    Rutgers The State University of New Jersey - New Brunswick.;

  • 授予单位 Rutgers The State University of New Jersey - New Brunswick.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 1993
  • 页码 197 p.
  • 总页数 197
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

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