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postgraduate thesis: Transition metal complexes with pyrazole and bulky salen ligands, catalysis, spectroscopic properties and bioactivity
Title | Transition metal complexes with pyrazole and bulky salen ligands, catalysis, spectroscopic properties and bioactivity |
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Authors | |
Advisors | Advisor(s):Che, CM |
Issue Date | 2016 |
Publisher | The University of Hong Kong (Pokfulam, Hong Kong) |
Citation | Chan, W. [陳偉文]. (2016). Transition metal complexes with pyrazole and bulky salen ligands, catalysis, spectroscopic properties and bioactivity. (Thesis). University of Hong Kong, Pokfulam, Hong Kong SAR. |
Abstract | 2,6-Bis[(4S, 7R)-7, 8, 8-trimethyl-4, 5, 6, 7-tetrahydro-4, 7-methano-1-indazoly]pyridine (PPz*) is a pincer ligand rarely used by chemists in the synthesis of transition metal complexes since its preparation is difficult. In this work, a new synthetic route to the compound was developed with safer and milder conditions. Iridium(III), palladium(II), platinum(II), cobalt(II) and silver(I) complexes supported with the PPz* ligand have been synthesized. Their luminescent and catalytic properties have been investigated. The iridium(III) carbene PPz* complex has been synthesized and studied by ESI-MS. The silver PPz* complex was found to catalyze cyclopropanation of styrenes and ethyl phenyldiazoacetate in good yields. A new methylated palladium(II) complex has been synthesized.
(+)-(Z)-3-(hydroxymethylene)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (HPz*), one of the starting materials for the synthesis of PPz*, bears a pyrazole ring, which can be also used as a ligand. The coinage metals, copper, silver and gold have been chosen to complex with HPz*. Their catalytic activities and anti-cancer properties have been investigated. The silver(I) HPz* complex was found to be an effective catalyst for intermolecular alkene cyclopropanation and sp3 C-H insertion to give corresponding products in good yields. Furthermore, it gives a better performance than cis-platin in killing cancer in cell line A2780, human ovarian carcinoma with IC50 7.21±0.29 μM.
Salen is one of the most common ligands used in transition metal catalysis. A novel bulky iron salen complex [FeIII(salen)Cl] (salen = N,N’-bis(2-CPh3-4-tBu-salicylidene)-1,2-cyclohexenediamine dianion) was synthesized by the reaction of the corresponding H2salen ligand and FeCl3. The complex structure was characterized by FAB-MS. Its catalytic activities toward carbene and nitrene transfer reactions were examined but it was found ineffective for these reactions. The Lewis acid catalysis with this complex is now being studied. |
Degree | Master of Philosophy |
Subject | Transition metal complexes |
Dept/Program | Chemistry |
Persistent Identifier | http://hdl.handle.net/10722/244315 |
DC Field | Value | Language |
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dc.contributor.advisor | Che, CM | - |
dc.contributor.author | Chan, Wai-man | - |
dc.contributor.author | 陳偉文 | - |
dc.date.accessioned | 2017-09-14T04:42:12Z | - |
dc.date.available | 2017-09-14T04:42:12Z | - |
dc.date.issued | 2016 | - |
dc.identifier.citation | Chan, W. [陳偉文]. (2016). Transition metal complexes with pyrazole and bulky salen ligands, catalysis, spectroscopic properties and bioactivity. (Thesis). University of Hong Kong, Pokfulam, Hong Kong SAR. | - |
dc.identifier.uri | http://hdl.handle.net/10722/244315 | - |
dc.description.abstract | 2,6-Bis[(4S, 7R)-7, 8, 8-trimethyl-4, 5, 6, 7-tetrahydro-4, 7-methano-1-indazoly]pyridine (PPz*) is a pincer ligand rarely used by chemists in the synthesis of transition metal complexes since its preparation is difficult. In this work, a new synthetic route to the compound was developed with safer and milder conditions. Iridium(III), palladium(II), platinum(II), cobalt(II) and silver(I) complexes supported with the PPz* ligand have been synthesized. Their luminescent and catalytic properties have been investigated. The iridium(III) carbene PPz* complex has been synthesized and studied by ESI-MS. The silver PPz* complex was found to catalyze cyclopropanation of styrenes and ethyl phenyldiazoacetate in good yields. A new methylated palladium(II) complex has been synthesized. (+)-(Z)-3-(hydroxymethylene)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (HPz*), one of the starting materials for the synthesis of PPz*, bears a pyrazole ring, which can be also used as a ligand. The coinage metals, copper, silver and gold have been chosen to complex with HPz*. Their catalytic activities and anti-cancer properties have been investigated. The silver(I) HPz* complex was found to be an effective catalyst for intermolecular alkene cyclopropanation and sp3 C-H insertion to give corresponding products in good yields. Furthermore, it gives a better performance than cis-platin in killing cancer in cell line A2780, human ovarian carcinoma with IC50 7.21±0.29 μM. Salen is one of the most common ligands used in transition metal catalysis. A novel bulky iron salen complex [FeIII(salen)Cl] (salen = N,N’-bis(2-CPh3-4-tBu-salicylidene)-1,2-cyclohexenediamine dianion) was synthesized by the reaction of the corresponding H2salen ligand and FeCl3. The complex structure was characterized by FAB-MS. Its catalytic activities toward carbene and nitrene transfer reactions were examined but it was found ineffective for these reactions. The Lewis acid catalysis with this complex is now being studied. | - |
dc.language | eng | - |
dc.publisher | The University of Hong Kong (Pokfulam, Hong Kong) | - |
dc.relation.ispartof | HKU Theses Online (HKUTO) | - |
dc.rights | The author retains all proprietary rights, (such as patent rights) and the right to use in future works. | - |
dc.rights | This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. | - |
dc.subject.lcsh | Transition metal complexes | - |
dc.title | Transition metal complexes with pyrazole and bulky salen ligands, catalysis, spectroscopic properties and bioactivity | - |
dc.type | PG_Thesis | - |
dc.description.thesisname | Master of Philosophy | - |
dc.description.thesislevel | Master | - |
dc.description.thesisdiscipline | Chemistry | - |
dc.description.nature | published_or_final_version | - |
dc.identifier.doi | 10.5353/th_991043953697003414 | - |
dc.date.hkucongregation | 2017 | - |
dc.identifier.mmsid | 991043953697003414 | - |