本論文主要探討銠卟啉和銥卟啉絡合物，分別與酮類與醛類進行的鍵活化化學。 / 第一部分主要介紹由β-乙基羥基銠卟啉絡合物(Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH)與酮類進行的羰基碳及α-碳(C(CO)-C(α)) 鍵活化(下稱碳碳鍵活化)。於室溫至50ºC時，在非溶劑的條件下，Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH選擇性地斷裂芳香酮和脂肪酮類的C(CO)-C(α)鍵，生成相對應的銠卟啉酰基絡合物(Rh{U+1D35}{U+1D35}{U+1D35}(ttp)COR, R = 烷基或芳基)，產率最高可達80%。作為銠卟啉羥基絡合物(Rh{U+1D35}{U+1D35}{U+1D35}(ttp)OH)的前體，Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH的活性展示出Rh{U+1D35}{U+1D35}{U+1D35}(ttp)OH是碳碳鍵活化的重要中間體。 / 第二部分主要介紹由β-乙基羥基銥卟啉絡合物(Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH)與芳香醛類進行，具選擇性的醛碳氫鍵活化。在160ºC和非溶劑的條件下，Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH與芳香醛類反應，生成相對應的銥卟啉酰基絡合物(Ir{U+1D35}{U+1D35}{U+1D35}(ttp)COAr)作為碳氫鍵活化產物，產率最高可達72%。銥卟啉羥基絡合物(Ir{U+1D35}{U+1D35}{U+1D35}(ttp)OH)和乙烯配位銥卟啉絡合正離子((CH₂=CH₂)Ir{U+1D35}{U+1D35}{U+1D35}(ttp)⁺)被推斷為醛碳氫鍵活化的可能中間體。 / This research focuses on the bond activation chemistry by rhodium and iridium porphyrin complexes with ketones and aldehyde respectively. / Part 1 describes the C(CO)-C(α) bond activation (CCA) of ketones by Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH (ttp = 5,10,15,20-tetratolylporphyrinato dianion). Rh{U+1D35}{U+1D35}{U+1D35}(ttp)- CH₂CH₂OH selectively cleaved the C(CO)-C(α) bond of aromatic and aliphatic ketones in solvent-free conditions at room temperature to 50ºC, giving the corresponding rhodium(III) porphyrin acyls (Rh{U+1D35}{U+1D35}{U+1D35}(ttp)COR, R = alkyl or aryl) up to 80% yield. The activity of the Rh{U+1D35}{U+1D35}{U+1D35}(ttp)OH precursor, Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH, demonstrates Rh{U+1D35}{U+1D35}{U+1D35}(ttp)OH as the key intermediate in the CCA of ketones. / [With images]. / Part 2 describes the selective aldehydic carbon-hydrogen bond activation (CHA) of aryl aldehydes by Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH. Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH reacted with aryl aldehydes in solvent-free conditions at 160ºC to give the corresponding iridium(III) porphyrin acyls (Ir{U+1D35}{U+1D35}{U+1D35}(ttp)COAr) as the CHA products up to 72% yield. Ir{U+1D35}{U+1D35}{U+1D35}(ttp)OH and (CH₂=CH₂)Ir{U+1D35}{U+1D35}{U+1D35}(ttp)⁺ were proposed as the possible intermediate for the CHA reaction. / [With images]. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Chan, Chung Sum. / "November 2012." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Abstracts also in Chinese. / Abstract --- p.i / Acknowledgement --- p.iii / Table of Contents --- p.iv / Abbreviations --- p.vii / Structural Abbreviations of Porphyrin --- p.viii / Chapter Part 1 --- Carbon-Carbon Bond Activation of Ketones with Rhodium(III) Porphyrin β-Hydroxyethyl --- p.1 / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Properties of Ketones --- p.1 / Chapter 1.2 --- Carbon(CO)-Carbon(α) Bond Activation (CCA) of Ketones --- p.2 / Chapter 1.2.1 --- CCA of Ketones by Transition Metal Complexes --- p.2 / Chapter 1.2.2 --- CCA of Ketones by Metalloporphyrins --- p.5 / Chapter 1.3 --- Porphyrin Ligands and Rhodium(III) Porphyrins --- p.7 / Chapter 1.3.1 --- Porphyrin Ligands --- p.7 / Chapter 1.3.2 --- Rhodium(III) Porphyrins --- p.8 / Chapter 1.4 --- Rhodium(III) Porphyrin Hydroxide --- p.10 / Chapter 1.4.1 --- Nature of Bonding in Late Transition Metal Hydroxides --- p.10 / Chapter 1.4.1.1 --- Hard-Soft Acid-Base principle --- p.11 / Chapter 1.4.1.2 --- dπ-pπ Interaction Model --- p.11 / Chapter 1.4.1.3 --- E-C Model --- p.12 / Chapter 1.4.2 --- Attempted Preparation of Rhodium(III) Porphyrin Hydroxides --- p.13 / Chapter 1.4.3 --- Chemistry of Rhodium(III) Porphyrin Hydroxides --- p.15 / Chapter 1.5 --- Rhodium(III) Porphyrin β-hydroxyethyl as Rhodium(III) Hydroxide Precursor --- p.18 / Chapter 1.6 --- Objective --- p.20 / Chapter Chapter 2 --- Carbon-Carbon Bond Activation of Ketones with Rhodium(III) Porphyrin β-Hydroxyethyl --- p.21 / Chapter 2.1 --- Preparation of Starting Materials --- p.21 / Chapter 2.1.1 --- Synthesis of Porphyrin --- p.21 / Chapter 2.1.2 --- Synthesis of Rhodium(III) Porphyrins --- p.21 / Chapter 2.2 --- CCA of Diisopropyl Ketone by Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH --- p.22 / Chapter 2.3 --- Optimization of Reaction Conditions --- p.22 / Chapter 2.3.1 --- Atmosphere Effect --- p.22 / Chapter 2.3.2 --- PPh3 Effect --- p.23 / Chapter 2.3.3 --- Solvent Effect --- p.24 / Chapter 2.4 --- Substrate Scope --- p.26 / Chapter 2.4.1 --- CCA of Isopropyl Ketones --- p.26 / Chapter 2.4.2 --- CCA of Non-Isopropyl Ketones --- p.28 / Chapter 2.5 --- Proposed Mechanism --- p.29 / Chapter 2.6 --- Comparison on CCA of Ketones by Different Rh{U+1D35}{U+1D35}{U+1D35}(por)OH Sources --- p.31 / Chapter 2.6.1 --- Reaction Conditions --- p.31 / Chapter 2.6.2 --- Substrate Scope --- p.32 / Chapter 2.6.3 --- Regioselectivity --- p.33 / Chapter 2.7 --- Comparison on Bond Activation of Carbonyl Compounds by Rhodium Porphyrin β-Hydroxyethyl --- p.34 / Chapter 2.8 --- CCA of Ketones with Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH --- p.36 / Chapter 2.9 --- Conclusion --- p.37 / Chapter Chapter 3 --- Experimental Sections --- p.39 / References --- p.54 / List of Spectra I --- p.59 / Spectra --- p.60 / Chapter Part 2 --- Aldehydic Carbon-Hydrogen Bond Activation with Iridium(III) Porphyrin β-Hydroxyethyl --- p.63 / Chapter Chapter 1 --- Introduction --- p.63 / Chapter 1.1 --- Properties of Aldehydes --- p.63 / Chapter 1.2 --- Carbon-Hydrogen Bond Activation (CHA) of Aldehydes --- p.64 / Chapter 1.2.1 --- CHA of Aldehydes by Transition Metal Complexes --- p.64 / Chapter 1.2.2 --- Aldehydic CHA by Metalloporphyrins --- p.74 / Chapter 1.3 --- Iridium(III) Porphyrins --- p.77 / Chapter 1.4 --- Iridium(III) Porphyrin Hydroxide --- p.78 / Chapter 1.4.1 --- Attempted Preparation of Iridium(III) Porphyrin Hydroxides --- p.78 / Chapter 1.4.2 --- Chemistry of Iridium(III) Porphyrin Hydroxides --- p.81 / Chapter 1.5 --- Iridium(III) Porphyrin β-hydroxyethyl as Iridium(III) Hydroxide Precursor --- p.83 / Chapter 1.6 --- Objective --- p.85 / Chapter Chapter 2 --- Aldehydic Carbon-Hydrogen Bond Activation with Iridium(III) Porphyrin β-Hydroxyethyl --- p.86 / Chapter 2.1 --- Preparation of Iridium(III) Porphyrins --- p.86 / Chapter 2.2 --- Aldehydic CHA of Benzaldehyde by Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH --- p.87 / Chapter 2.3 --- Optimization of Reaction Conditions --- p.87 / Chapter 2.3.1 --- Temperature Effect --- p.87 / Chapter 2.3.2 --- Solvent Effect --- p.88 / Chapter 2.3.3 --- PPh₃ Effect --- p.90 / Chapter 2.4 --- Substrate Scope --- p.93 / Chapter 2.5 --- Proposed Mechanism --- p.94 / Chapter 2.6 --- Conclusion --- p.96 / Chapter Chapter 3 --- Experimental Sections --- p.97 / References --- p.108 / List of Spectra II --- p.112 / Spectra --- p.112
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_328580 |
| Date | January 2013 |
| Contributors | Chan, Chung Sum., Chinese University of Hong Kong Graduate School. Division of Chemistry. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, bibliography |
| Format | electronic resource, electronic resource, remote, 1 online resource (viii, 114 leaves) : ill. |
| 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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