| DC 欄位 |
值 |
語言 |
| DC.contributor | 化學學系 | zh_TW |
| DC.creator | 彭峻嶸 | zh_TW |
| DC.creator | Chun-Jung Peng | en_US |
| dc.date.accessioned | 2016-8-10T07:39:07Z | |
| dc.date.available | 2016-8-10T07:39:07Z | |
| dc.date.issued | 2016 | |
| dc.identifier.uri | http://ir.lib.ncu.edu.tw:88/thesis/view_etd.asp?URN=103223059 | |
| dc.contributor.department | 化學學系 | zh_TW |
| DC.description | 國立中央大學 | zh_TW |
| DC.description | National Central University | en_US |
| dc.description.abstract | 在有機金屬化學中，配位基在反應中扮演重要的角色，可影響中心金屬的電子以及立體效應。同碳雙碳烯或稱為彎曲型重烯在配位基設計與有機金屬科學領域上，屬於新穎的分支，然而，其在催化反應的應用上仍有侷限，起因於缺乏有效的合成策略。本篇論文中我們成功的發展新的反應途徑，利用片段組合的概念合成出同碳雙碳烯，此種方法使我們能夠擴展其之骨架多樣性以及建立新的想法合成非對稱之同碳雙碳烯，並且針對其X-ray晶體結構及銠錯合物的光譜進行分析。
我們也證明同碳雙碳烯可作為二氧化碳為碳來源之胺基甲基化的有機催化劑，在此反應中，成功分離出具有獨特的硼氫活化之同碳雙碳烯硼錯合物，我們認為此活化物應為反應中間體，並以此證明胺基甲基化之反應機構。此獨特活化物也給了我們如何證明同碳雙碳烯是否為Frustrated Lewis Pair (FLP) 之靈感，證明硼烷、矽烷等小分子活化都可展現出同碳雙碳烯的FLP性質。 | zh_TW |
| dc.description.abstract | In Organometallic Chemistry, ligand which plays an important role in the reaction can influence electron properties and steric environment of a metal complex. Carbodicarbene or so-called bent allene stands out as a new branch of field in ligand-design and organometallic science. Its implication in the catalysis remains limited due to lack of effective synthesis strategy. In this thesis, we successfully develop a simple synthetic approach of carbodicarbene inspired by an organic SN2 reaction. This approach allow us to increase the diversity of a framework as well as to to establish a new conceptual of constructing unsymmetrical carbodicarbene. We have investigated structural analysis and spectroscopic studies of these ligands and their ligation Rh complexes. We also demonstrated that carbodicarbenes can act as organocatalysts for mediating amine methylation using CO2 as a C1 carbon source. The unique B-H-activate boron–carbodicarbene complex was isolated to be an intermediate of the reaction and provide the insight about mechanism of methylation reaction. The distinct reaction of borane complex have also led us to hyphotheize the carbodicarbene could act as Frustrated Lewis Pair (FLP). Small molecules activation like borane and silane has illustrated the possible FLP character in carbodicarbene. | en_US |
| DC.subject | 碳烯配位基 | zh_TW |
| DC.subject | 同碳雙碳烯 | zh_TW |
| DC.subject | 二氧化碳活化 | zh_TW |
| DC.subject | 有機催化 | zh_TW |
| DC.subject | carbene ligands | en_US |
| DC.subject | carbodicarbenes | en_US |
| DC.subject | CO2 activation | en_US |
| DC.subject | organocatalysis | en_US |
| DC.title | 開發骨架多樣性的同碳雙碳烯及直接觀察硼氫活化促使胺類與二氧化碳進行甲基化反應 | zh_TW |
| dc.language.iso | zh-TW | zh-TW |
| DC.title | Expanding Ligand Framework Diversity of Carbodicarbenes and Direct Detection of Boron Activation in Methylation of Amines with CO2 | en_US |
| DC.type | 博碩士論文 | zh_TW |
| DC.type | thesis | en_US |
| DC.publisher | National Central University | en_US |