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Synthesis and reactivity of mixed metallocene cyclopentadienyl cyclooctatetraenyl uranium complexes.

机译：混合茂金属环戊二烯基环辛酸酯四烯基铀配合物的合成与反应性。

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摘要

This dissertation describes the investigation of the organometallic chemistry of uranium complexes with ligand environments alternative to the ubiquitous [(C5Me5)2]2- ligand set found in so many organometallic complexes. Specifically, the effect on uranium chemistry of replacing one (C5Me5)1- ligand with (C8H8)2- was probed. The resulting [(C 5Me5)(C8H8)]3- ligand set has been used as a platform to synthesize [(C5Me5)( 8H8)U]1+ complexes and investigate their unusual reactivity.;Chapter 1 describes the reductive reactivity of [(C5Me 5)(C8H8)U]2(mu -C8H8) with PhEEPh (E = S, Se, and Te), phenazine, and nitrobenzene. The results in this chapter constitute the only examples of the (C8H8)2- ligand being used for ligand-based reduction.;Chapter 2 describes the synthesis of [(eta 5-C5Me5)(eta8-C 8H8)U(mu-OTf)]2 (OTf = OSO 2CF3) by taking advantage of the ligand-based reduction described in Chapter 1. [(eta5-C5Me 5)(eta8-C8H8)U( mu-OTf)]2 is a convenient precursor for generating [(C 5Me5)(C8H8)U]1+ alkyl and aryl complexes including the first stable uranium metallocene phenyl complex.;Chapter 3 describes the synthesis of highly reactive, sterically unsaturated uranium monoalkyl complexes (C5Me5)(C8H 8)UR that decompose in solution to form a unique tuck-in uranium complex (eta8-C8H8)(eta5:eta 1-C5Me4CH2)U. The reactivity of this tuck-in complex is examined with substrates known to insert into U-C bonds including iPrN=C=NiPr, tBuN≡C, and C≡O.;Chapter 4 describes studies related to the reaction of (C5Me 5) 3U with C8H8 to form [(C5Me 5)(C8H8)U]2(mu-C 8H8). This is the only example of multiple SIR reactions occurring from a single molecule. This Chapter describes the formation of a series of bis(cyclopentadienyl) cyclooctatetraenyl dianion uranium complexes which support the formation of [(C5Me5)(C8H 8)U]2(mu-C8H8) through a "(C5Me5)2(C8H8)U" intermediate via sterically induced reduction (SIR).;Chapter 5 describes the examination of the uranium bipyridine complexes [(eta5-C5Me5)( eta8-C8H8)U(bipy- kappa2N,N') (bipy = 2,2'-bipyridine) and [(eta5-C5Me5)( eta8-C8H8)U(Me2bipy- kappa2N,N') (Me2bipy = 4,4'-dimethyl-2,2'-bipyridine) to determine if they contain neutral bipyridine bound to a U3+ or bipyridyl radical anion bound to a U4+ metal center. X-ray crystallography, infrared spectroscopy, and density functional theory calculations were employed to determine the oxidation state of uranium.
机译：这篇论文描述了铀配位体的有机金属化学的研究，该配位体环境替代了在许多有机金属配合物中普遍存在的[（C5Me5）2] 2-配体集。具体而言，探讨了用（C8H8）2-取代一种（C5Me5）1-配体对铀化学的影响。所得的[（C 5Me5）（C8H8）] 3-配体组已用作合成[（C5Me5）（8H8）U] 1+配合物并研究其异常反应性的平台。第一章介绍了[ （C5Me 5）（C8H8）U] 2（μ-C8H8）与PhEEPh（E = S，Se和Te），吩嗪和硝基苯。本章中的结果构成（C8H8）2-配体用于基于配体还原的唯一实例。;第二章介绍了[（eta 5-C5Me5）（eta8-C 8H8）U（mu-OTf）的合成）] 2（OTf = OSO 2CF3），它利用了第1章中所述的基于配体的还原。[（eta5-C5Me 5）（eta8-C8H8）U（mu-OTf）] 2是产生[ （C 5Me5）（C8H8）U] 1+烷基和芳基配合物，包括第一个稳定的铀茂金属苯基配合物。;第3章描述了高活性，空间不饱和铀单烷基配合物（C5Me5）（C8H 8）UR的合成溶液形成独特的t入铀络合物（eta8-C8H8）（eta5：eta 1-C5Me4CH2）U。用已知插入UC键的底物（包括iPrN = C = NiPr，tBuN≡C和C = O）检验了这种插入复合物的反应性。第4章描述了与（C5Me 5）3U与C8H8形成[（C5Me 5）（C8H8）U] 2（mu-C 8H8）。这是单个分子发生多个SIR反应的唯一例子。本章描述了一系列双（环戊二烯基）环辛酸四烯基二价铀络合物的形成，这些络合物通过“（C5Me5）2（C8H8）U”支持[（C5Me5）（C8H 8）U] 2（mu-C8H8）的形成。第五章描述了铀联吡啶络合物[（eta5-C5Me5）（eta8-C8H8）U（bipy- kappa2N，N'）（bipy = 2,2'-bipyridine）的检测和[（eta5-C5Me5）（eta8-C8H8）U（Me2bipy- kappa2N，N'）（Me2bipy = 4,4'-二甲基-2,2'-联吡啶）确定它们是否含有与U3 +结合的中性联吡啶联吡啶基阴离子与U4 +金属中心键合。 X射线晶体学，红外光谱和密度泛函理论计算被用来确定铀的氧化态。

著录项

  • 作者

    Takase, Michael K.;

  • 作者单位

    University of California, Irvine.;

  • 授予单位 University of California, Irvine.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2009
  • 页码 127 p.
  • 总页数 127
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

  • 入库时间 2022-08-17 11:38:31

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