本文成功地合成了碳碳相連的鳥巢型碳硼烷化合物[Me₃NH][7,8-O(CH₂)₂-7,8-C₂B₉H₁₀]，閉籠型碳硼烷衍生物1-(1-茚基)-1,2-碳硼烷以及一系列基於以上配體的稀土金屬配合物，同時研究並探討了這些化合物對不同不飽和有機化合物的反應性。 / 1-(1-茚基)-1,2-碳硼烷可通過碳硼烷二鋰鹽與相應環氧化合物反應後再脫水而製備。該配體與稀土烷基化合物發生酸碱反應生成相應的稀土碳硼烷化合物，[η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ (Ln= Y, Gd, Er, Dy)。這類稀土碳硼烷化合物的反應性也被相繼研究。它可以跟各種不飽和底物（如碳二亞胺，異氰，異硫氰酸鹽，異氰酸酯）反應。其中和R-N=C=N-R (R= TMS, tBu) 反应生成相應的單插入產物。这些单插入产物可以继续和小分子反应插入稀土金屬碳硼烷碳鍵得到双插入产物。並且，這類稀土碳硼烷化合物也可以發生質子化反應生成對應的離子型化合物。 / [Me₃NH][7,8-O(CH₂)₂-7,8-C₂B₉H₁₀]可通過(CH₂OCH₂)C₂B₁₀H₁₀的脫硼反應製備，它與Ln(CH₂-o-C₆H₄-NMe₂)₃ (Ln = Y, Gd, Er, Dy)反應得到半夾心金屬碳硼烷 [η⁵-(CH₂OCH₂)C₂B₉H₉]Ln(CH₂-o-C₆H₄-NMe₂)(THF)₂.不飽和的極性有機不飽合底物可以插入金屬碳鍵，并在取代基的空間位阻效應的影響下生成單插入或者雙插入的產物。 / 該論文中也研究了[η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂和[η⁵-(CH₂OCH₂)C₂B₉H₉]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂與不同的Brønsted酸的酸堿反應。[η⁵-(CH₂OCH₂)C₂B₉H₉]Y[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ 同各種各樣的胍反應生成相應的胍基化合物。 / 最後，1-(1-茚基)-1,2-碳硼烷發生脫硼反應可生成對應的[Me₃NH][(C₉H₇)C₂B₉H₁₁]。該配體同Y(CH₂-o-C₆H₄-NMe₂)₃反應得到的稀土烷基化合物[(1-C₉H₆)(C₂B₉H₁₀)]Y(DME)₂也進一步的進行了研究。它同二苯酮，二苯基乙烯酮，二（2-吡啶基）甲酮以及其他不飽和有機化合物反應，得到具有類似結構的單插入產物。 / C,C'-Linked dicarbollide species [Me₃NH][7,8-CH₂OCH₂-7,8-C₂B₉H₁₀] and 1-(1-indenyl)-1,2-carborane were synthesized. Their applications in rare earth chemistry were studied and discussed in this thesis. / 1-(1-Indenyl)-1,2-carborane was synthesized from the reaction of indene epoxide with dilithium salt of carborane. Reaction of this ligand with Ln(CH₂C₆H₄-o-NMe₂)₃ (Ln = Y, Gd, Er, Dy) led to the formation of [η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ (Ln= Y, Gd, Er, Dy). The metal-carbon σ bond in these complexes was reactive toward unsaturated polar organic substrates, such as carbodiimide, isocyanide, isothiocyanate, and isocynate. They reacted with R-N=C=N-R (R= TMS, tBu) to form mono-insertion products. The metal-cage carbon σ bond in the mono-insertion product was also active toward unsaturated polar organic substrates to form di-insertion complexes. And the indenyl-carboranyl gadolinium complex can be protonated to give ionic species. / [Me₃NH][7,8-CH₂OCH₂-7,8-C₂B₉H₁₀] was prepared by the deboration reaction of (CH₂OCH₂)C₂B₁₀H₁₀. Ln(CH₂C₆H₄-o-NMe₂)₃ (Ln = Y, Gd, Er) reacted with this ligand to form half-sandwich metallacarboranes [η⁵ -(CH₂OCH₂)C₂B₉H₉]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂. Unsaturated polar organic substrates, such as isocyanide, isothiocyanate, and isocynate can insert into the M-C bond to form mono-insertion complexes or di-insertion complexes depending on the steric factor of the substrate. / Acid-base reactions of [η⁵:σ-(C₉H₆)C₂B₁₀H₁₀]Ln[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ and [σ:η⁵-O(CH₂)₂C₂B₉H₉]Y[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ were studied. Complex [σ:η⁵-O(CH₂)₂C₂B₉H₉]Y[σ:σ-(CH₂C₆H₄-o-NMe₂)](THF)₂ reacted with various guanidines to give the corresponding guanidinato products. / Complex [(1-C₉H₆)(C₂B₉H₁₀)]Y(DME)₂ was synthesized and structurally characterized from the reaction of [Me₃NH][(C₉H₇)C₂B₉H₁₁] with Y(CH₂-o-NMe₂-C₆H₄)₃ in DME. Its reactivity was examined. It reacted with diphenylketone, diphenylketene, di(2-pyridyl)ketone and other unsaturated organic compounds to afford mono-insertion products with similar structures. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Yang, Jingying. / Thesis (Ph.D.) Chinese University of Hong Kong, 2014. / Includes bibliographical references (leaves 113-124). / Abstracts also in Chinese.
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_1077723 |
| Date | January 2014 |
| Contributors | Yang, Jingying (author.), Xie, Zuowei (thesis advisor.), Chinese University of Hong Kong Graduate School. Division of Chemistry, (degree granting institution.) |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, bibliography, text |
| Format | electronic resource, electronic resource, remote, 1 online resource (xviii, 131 leaves) : illustrations, computer, online resource |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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