Metal complexes derived from chelating amido ligands.

by Cheng Pui Shan.Thesis (M.Phil.)--Chinese University of Hong Kong, 2004.Includes bibliographical references.Abstracts in English and Chinese.Abstract --- p.i摘要 --- p.iiiAcknowledgement --- p.ivTable of Contents --- p.vList of Compounds --- p.viiiAbbreviations --- p.xiChapter Chapter 1. --- A General introduction to Metal amidesChapter 1.1 --- introductionChapter 1.1.1 --- General Background --- p.1Chapter 1.1.2 --- Metal Complexes with 2-Pyridyl Amido Ligands --- p.2Chapter 1.2 --- OBJECTIVES OF THIS WORK --- p.4Chapter 1.3 --- references for chapter1 --- p.5Chapter Chapter 2. --- Group 13 metal AmidesChapter 2.1 --- GENERAL BACKGROUND --- p.8Chapter 2.1.1 --- Common Methods for the Preparation of Group 13 Metal Amides --- p.8Chapter 2.1.2 --- "An Overview on Aluminum(III), Gallium(III) and Indium(III) Amides" --- p.9Chapter 2.1.3 --- An Overview on Aluminum(III) Aryloxides --- p.15Chapter 2.2 --- aims of our studies --- p.18Chapter 2.3 --- results and discussion --- p.19Chapter 2.3.1 --- Preparation of [HN(SiButMe2)(2-C5H3N-6-Me)] (HL1) and Its Lithium Derivative [LiL1(TMEDA)] --- p.19Chapter 2.3.2 --- "Synthesis and Structures of Aluminum(III), Gallium(III) and Indium(III) Amides"Chapter 2.3.2.1 --- "Synthesis of [MCl(L1)2] (M = Al 3, Ga 4) and [In(L1)3] (5)" --- p.20Chapter 2.3.2.2 --- Physical Characterization of Compounds 3-5 --- p.21Chapter 2.3.2.3 --- Molecular Structures of Compounds 3-5 --- p.24Chapter 2.3.3 --- Reactivity Studies --- p.35Chapter 2.3.3.1 --- Physical Characterization of Compounds 6 and7 --- p.38Chapter 2.3.3.2 --- Molecular Structures of Compounds 6 and7 --- p.39Chapter 2.4 --- EXPERIMENTALS FOR CHAPTER2 --- p.47Chapter 2.5 --- REFERENCES FOR CHAPTER2 --- p.52Chapter Chapter 3. --- A Silyl´ؤlinked diamine compound and its metal complexesChapter 3.1 --- A GENERAL INTRODUCTION TO DIAMINE COMPOUNDS --- p.59Chapter 3.2 --- A GENERAL INTRODUCTION TO MIXED ALKALI METAL AMIDES --- p.65Chapter 3.3 --- AIMS OF OUR STUDIES --- p.67Chapter 3.4 --- SYNTHESIS AND STRUCTURES OF [Me2Si{NH(2-Py)}2] AND THE CORRESPONDING ALKALI METAL AMIDESChapter 3.4.1 --- Synthesis and Structure of [Me2Si{NH(2-Py)}2] (HL2) (8) --- p.68Chapter 3.4.2 --- Synthesis and Structures of Alkali Metal AmidesChapter i. --- Synthesis of Sodium Derivatives of8 --- p.74Chapter ii. --- Synthesis of a Mixed Alkali Metal Derivative of8 --- p.75Chapter iii. --- Attempted Metallation of 8 with KBun --- p.75Chapter iv. --- Physical Characterization --- p.77Chapter v. --- Molecular Structures --- p.80Chapter 3.5 --- synthesis and structure of the iron(ii) derivative [Fe(L2)Cl]2Chapter 3.5.1 --- An Overview on Iron(II) Amides --- p.95Chapter 3.5.2 --- Aims of Our Studies --- p.97Chapter 3.5.3 --- Synthesis and Structure of [FeCl(L2)]2 (14)Chapter i. --- Synthesis and Characterization --- p.98Chapter ii. --- Molecular Structure --- p.99Chapter 3.6 --- EXPERIMENTALS FOR CHAPTER 3 --- p.102Chapter 3.7 --- REFERENCES FOR CHAPTER 3 --- p.106APPENDIX 1General Procedures and Physical Measurements --- p.110X-Ray Crystallography --- p.110APPENDIX 2Table A-1. Selected crystallographic data for compounds 3-5. --- p.113Table A-2. Selected crystallographic data for compounds 6´ؤ7. --- p.114Table A-3. Selected crystallographic data for compounds 8，10-11. --- p.115Table A-4. Selected crystallographic data for compounds 12-14. --- p.11

Synthetic and structural studies of groups 4-6 transition metal amides and amidinates.

Lam, Pui Chi.Thesis submitted in: November 2006.Thesis (M.Phil.)--Chinese University of Hong Kong, 2007.Includes bibliographical references.Abstracts in English and Chinese.Table of Contents --- p.iAcknowledgements --- p.vAbstract --- p.vi摘要 --- p.viiiList of Compounds --- p.xAbbreviations --- p.xiiiChapter CHAPTER 1. --- A GENERAL INTRODUCTION TO METAL AMIDESChapter 1.1 --- GENERAL BACKGROUND --- p.1Chapter 1.2 --- OBJECTIVES OF THIS WORK --- p.7Chapter 1.3 --- REFERENCES FOR CHAPTER1 --- p.8Chapter CHAPTER 2. --- SYNTHESIS AND STRUCTURES OF GROUP 4 METAL AMIDESChapter 2.1 --- INTRODUCTION --- p.15Chapter 2.1.1 --- General Background --- p.15Chapter 2.1.2 --- Common Preparation Methods for Group 4 Metal Amides --- p.15Chapter 2.1.3 --- "An Overview on Titanium(IV), Zirconium(IV) and Hafnium(IV) Amides" --- p.17Chapter 2.2 --- AIMS OF OUR STUDIES --- p.26Chapter 2.3 --- RESULTS AND DISCUSSION --- p.27Chapter 2.3.1 --- Synthesis of the Ligand Precursor (HL1) and the Corresponding Lithium Derivative [Li(L1tmeda)] --- p.27Chapter 2.3.2 --- Synthesis and Structures of Monomeric and Dimeric Titanium(IV) Amides --- p.28Chapter 2.3.2.1 --- Synthesis of [Ti(L1 )Cl2(μ-Cl)2] (V and [TiL1)Ch3(THF)] (4) --- p.28Chapter 2.3.2.2 --- Reactivity Studies --- p.31Chapter 2.3.2.3 --- Physical Characterization of Compounds 3 and 4 --- p.33Chapter 2.3.2.4 --- Molecular Structures of Compounds 3 and 4 --- p.36Chapter 2.3.3 --- Synthesis and Structures of Mononuclear Zirconium(IV) and Hafnium(IV) Amides --- p.44Chapter 2.3.3.1 --- Synthesis of[M(L1)3Cl] (M = Zr 5 and Hf6) --- p.44Chapter 2.3.3.2 --- Reactivity Studies --- p.45Chapter 2.3.3.3 --- Synthesis of[MCL1)3H] (M = Zr7 and Hf8) --- p.48Chapter 2.3.3.4 --- Reactivity Studies of Compound7 --- p.49Chapter 2.3.3.5 --- Physical Characterization of Compound 8 --- p.51Chapter 2.3.3.6 --- Molecular Structures of Compound 8 --- p.53Chapter 2.3.3.7 --- Synthesis of [Zr(L1)3Me] (9) --- p.57Chapter 2.3.3.8 --- Reactivity Studies of Compound 9 --- p.58Chapter 2.3.3.9 --- Physical Characterization of Compound 9 --- p.59Chapter 2.3.3.10 --- Molecular Structure of Compound 9 --- p.60Chapter 2.4 --- EXPERIMENTALS FOR CHAPTER 2 --- p.64Chapter 2.4.1 --- General Procedures --- p.64Chapter 2.4.2 --- Synthesis of Compounds --- p.65REFERENCES FOR CHAPTER 2 --- p.68Chapter CHAPTER 3. --- SYNTHESIS AND STRUCTURES OF VANADIUM(III) AMIDO AND BENZAMIDINATO COMPLEXESChapter 3.1 --- INTRODUCTION --- p.74Chapter 3.1.1 --- General Background --- p.74Chapter 3.1.2 --- A Brief Introduction on Metal Amidinates --- p.75Chapter 3.1.3 --- An Overview on Vanadium(III) Amides --- p.77Chapter 3.1.4 --- An Overview on Vanadium(III) Amidinates --- p.82Chapter 3.2 --- AIMS OF OUR STUDIES --- p.85Chapter 3.3 --- RESULTS AND DISCUSSION --- p.86Chapter 3.3.1 --- Synthesis and Structures of Dinuclear Vanadium(III) Amides --- p.86Chapter 3.3.1.1 --- Synthesis of[V(L1)2(μ~Cl)]2(10) --- p.86Chapter 3.3.1.2 --- Reactivity Studies --- p.88Chapter 3.3.1.3 --- Synthesis of [V(L1)2(μ-H)]2 (11) --- p.90Chapter 3.3.1.4 --- Physical Characterization of Compounds 10 and 11 --- p.90Chapter 3.3.1.5 --- Molecular Structures of Compounds 10 and 11 --- p.94Chapter 3.3.2 --- Synthesis and Structure of Mononuclear Vanadium(III) Benzamidinate --- p.102Chapter 3.3.2.1 --- "Synthesis of [Li(L2)(tmeda)] (13) (L2 = [PhC(NSiMe3) (NC6H3Me2-2, 6)])" --- p.102Chapter 3.3.2.2 --- Synthesis of [V(L2)2Cl] (14) and trans´ؤ[V(tmeda)2Cl2] (15) --- p.103Chapter 3.3.2.3 --- Reactivity Studies --- p.104Chapter 3.3.2.4 --- Physical Characterization of Compound 14 --- p.107Chapter 3.3.2.5 --- Molecular Structure of Compound 14 --- p.107Chapter 3.4 --- EXPERIMENTALS FOR CHAPTER 3 --- p.111Chapter 3.4.1 --- General Procedures --- p.111Chapter 3.4.2 --- Synthesis of Compounds --- p.112Chapter 3.5 --- REFERENCES FOR CHAPTER 3 --- p.115Chapter CHAPTER 4. --- SYNTHESIS AND STRUCTURES OF CHROMIUM AMIDO AND BENZAMIDINATO COMPLEXESChapter 4.1 --- INTRODUCTION --- p.122Chapter 4.1.1 --- General Background --- p.122Chapter 4.1.2 --- An Overview on Chromium(III) Amides --- p.122Chapter 4.1.3 --- An Overview on Chromium(II) Amidinates --- p.125Chapter 4.2 --- AIMS OF OUR STUDIES --- p.129Chapter 4.3 --- RESULTS AND DISCUSSION --- p.130Chapter 4.3.1 --- Synthesis and Structures of A Monomeric Chromium(III) Amide and A Chromium(II) Benzamidinate --- p.130Chapter 4.3.1.1 --- Synthesis of[Cr(L1)3] (16) --- p.130Chapter 4.3.1.2 --- Synthesis of [Cr(L2)2] (17) --- p.132Chapter 4.3.1.3 --- Physical Characterization of Compounds 16 and 17 --- p.133Chapter 4.3.1.4 --- Molecular Structures of Compounds 16 and 17 --- p.135Chapter 4.4 --- EXPERIMENT ALS FOR CHAPTER 4 --- p.141Chapter 4.4.1 --- General Procedures --- p.141Chapter 4.4.2 --- Synthesis of Compounds --- p.141Chapter 4.5 --- REFERENCES FOR CHAPTER 34 --- p.144APPENDIX 1Physical Measurements and X-Ray Crystallography --- p.147APPENDIX 2"Mass Spectra, 1'H and 13C{]H} NMR Spectra, and IR Spectra" --- p.148APPENDIX 3 --- p.172Table A-1. Selected crystallographic data for compounds 3-4 --- p.173Table A-2. Selected crystallographic data for compounds 8-9 --- p.174Table A-3. Selected crystallographic data for compounds 10-11 --- p.175Table A-4. Selected crystallographic data for compounds 14，16-17 --- p.17

Catalytic Applications of Pyridine-Containing Macrocyclic Complexes

The introduction of a pyridine moiety into the skeleton of a polyazamacrocyclic ligand affects both the thermodynamic properties and the coordination kinetics of the resulting metal complexes. These features have attracted great interest from the scientific community in recent years. The field of application of pyridine-containing macrocyclic ligands ranges from biology to supramolecular chemistry, encompassing MRI, molecular recognition, materials and catalysis. In this microreview we provide a perspective of the catalytic applications of metal complexes of pyridine-containing macrocycles, including an account of investigations from the authors' laboratories dealing with stereoselective C\u2013C and C\u2013O bond-forming reactions. The increased conformational rigidity imposed by the pyridine ring allowed for the isolation and characterisation of metal complexes in high oxidation states and the study of their relevance in oxidation reactions. On the other hand, the very different conformations accessible upon the metal coordination and the easily tuneable synthesis of the macrocyclic ligands have been exploited in stereoselective synthesis

Syntheses of novel acyclic amino-amido ligands

Bibliography: page 154.Towards the labelling of biological macromolecules in contrast media, a synthesis of the novel bifunctional amido-ligands N,N' -bis[2-(N'',N''-dimethylamino)ethyl]-4-aminobenzylmalondiamide (67) and the 3-aminopropyl derivative (66) from appropriately C-functionalized malonates by amidation with N,N-dimethylethylenediamine (62) followed by reduction of the respective nitro (64) and cyano (63) groups is described. The synthesis of N,N'-bis[2-(N'',N''-dimethylamino)ethyl]iminodiacetamide (73) from diethyl N-benzyliminodiacetate (79) by amidation· with (62) followed by debenzylation is described. Herein is also reported the unsuccessful attempts to prepare a functionalized pentaamine ligand similar to (73) via the intermediacy of N,N'-bis[2-(N'',N''-dimethylamino)ethyl]-N'''-(2,2-diethoxyethyl) iminodiacetamide (112) whose preparation is also detailed. Attempts to this end via the Mitsunobu and Steglich coupling of N,N' -bis[2-(N'',N''- dimethylamino)ethyl]-N'''-(2-hydroxyethyl)iminodiacetamide (100) with N-tertbutyloxycarbonylglycine (105) also met with failure .. Further failed attempts to secure suitably functionalized intermediates by N-alkylation of diethyl iininodiacetate (70) with appropriate electrophiles are described. The successful functionalization of the pentaamine series of ligands by N-alkylation of (73) withpnitrobenzoyl chloride (118) to give N,N' -bis[2-(N'',N''- dimethylamino)ethyl] N''' -(4-nitrobenzamido)iminodiacetamide (119) is presented. The preparation of the non-functionalized novel trioxo heptaamine ligand N,N' ,N''-tris[2-(N'',N''-dimethylamino)ethyl]nitrilotriacetamide hydrochloride (86a) is also described. An investigative study towards the assembly of a novel triamine system for encapsulating NMR or isotopic NMR-active metal ions for possible use in diagnostic medicine is reported. The key facet to this end is the reported preparation of N,N' ,N''-tris(2-aminoethyl)propane-1,2,3-tricarboxamide (89) by controlled amidation of trimethyl propane 1,2,3-tricarboxylate (88) with ethylenediamine. The syntheses of functionalized and non-functionalized novel tetraamine dioxo and trioxo ligands from glycine, ethyl N-benzylglycinate (78), L-valine, and L-lysine via classical peptide synthesis methodology (in part) are described

Metal Catalyzed Group 14 And 15 Bond Forming Reactions: Heterodehydrocoupling And Hydrophosphination

Investigation of catalytic main-group bond forming reactions is the basis of this dissertation. Coupling of group 14 and 15 elements by several different methods has been achieved. The influence of Si–N heterodehydrocoupling on the promotion of α-silylene elimination was realized. Efficient Si–N heterodehydrocoupling by a simple, earth abundant lanthanide catalyst was demonstrated. Significant advances in hydrophosphination by commercially available catalysts was achieved by photo-activation of a precious metal catalyst. Exploration of (N3N)ZrNMe2 (N3N = N(CH2CH2NSiMe3)33–) as a catalyst for the cross-dehydrocoupling or heterodehydrocoupling of silanes and amines suggested silylene reactivity. Further studies of the catalysis and stoichiometric modeling reactions hint at α-silylene elimination as the pivotal mechanistic step, which expands the 3p elements known to engage in this catalysis and provides a new strategy for the catalytic generation of low-valent fragments. In addition, silane dehydrocoupling by group 1 and 2 metal bis(trimethylsilyl)amide complexes was investigated. Catalytic silane redistribution was observed, which was previously unknown for d0 metal catalysts. La[N(SiMe3)2]3THF2 is an effective pre-catalyst for the heterodehydrocoupling of silanes and amines. Coupling of primary and secondary amines with aryl silanes was achieved with a loading of 0.8 mol % of La[N(SiMe3)2]3THF2. With primary amines, generation of tertiary and sometimes quaternary silamines was facile, often requiring only a few hours to reach completion, including new silamines Ph3Si(nPrNH) and Ph3Si(iPrNH). Secondary amines were also available for heterodehydrocoupling, though they generally required longer reaction times and, in some instances, higher reaction temperatures. By utilizing a diamine, dehydropolymerization was achieved. The resulting polymer was studied by MS and TGA. This work expands upon the utility of f-block complexes in heterodehydrocoupling catalysis. Stoichiometric and catalytic P–E bond forming reactions were explored with ruthenium complexes. Hydrophosphination of primary phosphines and activated alkenes was achieved with 0.1 mol % bis(cyclopentadienylruthenium dicarbonyl) dimer, [CpRu(CO)2]2. Photo-activation of [CpRu(CO)2]2 was achieved with a commercially available UV-A 9W lamp. Preliminary results indicate that secondary phosphines as well as internal alkynes may be viable substrates with this catalyst. Attempts to synthesize ruthenium phosphinidene complexes for stoichiometric P–E formation have been met with synthetic challenges. Ongoing efforts to synthesize a ruthenium phosphinidene are discussed. The work in this dissertation has expanded the utility of metal-catalyzed main-group bond forming reactions. A potential avenue for catalytic generation low-valent silicon fragments has been discovered. Rapid Si–N heterodehydrocoupling by an easily obtained catalyst has been demonstrated. Hydrophosphination with primary phosphines has been achieved with a commercially available photocatalyst catalyst, requiring only low intensity UV light

Syntheses, structures and reactivities of bis(1-aza-allyl) and bis(phosphoranoimido) metal complexes.

Queenie Wai Yan Ip.Thesis (M.Phil.)--Chinese University of Hong Kong, 2003.Includes bibliographical references (leaves 91-94).Abstracts in English and Chinese.Acknowledgements --- p.iiAbstract --- p.iii摘要 --- p.vList of Abbreviations --- p.xiiList of Compounds Synthesized --- p.xiiiChapter CHAPTER 1 --- Syntheses and Characterizations of Pyrazyl-Linked Bis(l-Aza-Allyl) Alkali-Metal ComplexesChapter 1.1. --- Introduction --- p.1Chapter 1.1.1. --- A General Review of 1-Aza-Allyl Ligands --- p.1Chapter 1.1.2. --- A General Review of Group 1 Alkali-Metal Complexes Containing Bis(l-Aza-Allyl) Ligands --- p.6Chapter 1.2. --- Objective --- p.9Chapter 1.3. --- Results and Discussion --- p.11Chapter 1.3.1. --- Preparation and Characterization of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Lithium Complex --- p.11Chapter 1.3.1.1. --- "A Modified Synthesis of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Lithium Complex [Li2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}(THF)2]2 (1)" --- p.11Chapter 1.3.1.2. --- Physical and Spectroscopic Properties of Complex 1 --- p.11Chapter 1.3.1.3. --- Molecular Structure of Complex 1 --- p.12Chapter 1.3.2. --- Preparation and Characterization of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Sodium and Di-Potassium Complexes --- p.15Chapter 1.3.2.1. --- "Preparation of Pyrazyl-Linked Bis( 1 -Aza-Allyl) Di-Sodium complex [Na2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}(THF)2]2 (2) and Di-Potassium Complex [K2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}- (THF)3]2 (3)" --- p.15Chapter 1.3.2.2. --- Physical and Spectroscopic Properties of Complexes 2 and 3 --- p.15Chapter 1.3.2.3. --- Molecular Structures of Complexes 2 and 3 --- p.16Chapter 1.4 --- Experimental Section --- p.23Chapter 1.5 --- References --- p.25Chapter CHAPTER 2 --- Syntheses and Characterizations of Pyrazyl-Linked Bis(l-Aza-Allyl) Group 2 and 12 Metal ComplexesChapter 2.1 --- Introduction --- p.29Chapter 2.1.1. --- A General Review of Group 2 Metal Complexes containing Bis(l-Aza-Allyl) Ligands --- p.29Chapter 2.1.2. --- A General Review of Group 12 Metal Complexes containing Bis(l-Aza-Allyl) Ligands --- p.32Chapter 2.2 --- Results and Discussion --- p.34Chapter 2.2.1. --- Preparation and Characterization of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Magnesium Complex --- p.34Chapter 2.2.1.1. --- "Preparation of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Magnesium Complex [Mg2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}Br2(THF)4] (4).……" --- p.34Chapter 2.2.1.2. --- Physical and Spectroscopic Properties of Complex 4 --- p.34Chapter 2.2.1.3. --- Molecular Structure of Complex 4 --- p.35Chapter 2.2.2. --- Preparation and Characterization of Pyrazyl-Linked Bis(l-Aza-Allyl) Lithium Zincate Complex --- p.38Chapter 2.2.2.1. --- "Preparation of Pyrazyl-Linked Bis(l-Aza-Allyl) Lithium Zincate Complex [Zn2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}Cl2(u-Cl)2Li2(THF)6] (5)" --- p.38Chapter 2.2.2.2. --- Physical and Spectroscopic Properties of Complex 5 --- p.39Chapter 2.2.2.3. --- Molecular Structure of Complex 5 --- p.39Chapter 2.2.3. --- Preparation and Characterization of Unexpected Cyclization Compound --- p.42Chapter 2.2.3.1. --- "Preparation of Unexpected Cyclization Compound [{Me2Si{NC(But)C(H)}}2C4H2N2-2,3] (6)" --- p.42Chapter 2.2.3.2. --- Physical and Spectroscopic Properties of Complex 6 --- p.43Chapter 2.2.3.3. --- Molecular Structure of Complex 6 --- p.44Chapter 2.2.4. --- Attempted Synthesis of Analogous Mercury Complex --- p.45Chapter 2.2.5. --- Comparison on Structures and Reactivities of Compounds 4-6 --- p.46Chapter 2.3. --- Experimental Section --- p.48Chapter 2.4. --- References --- p.50Chapter CHAPTER 3 --- Syntheses and Characterizations of Bis(Phosphoranoimido) Magnesium and Group 14 Metal ComplexesChapter 3.1 --- Introduction --- p.52Chapter 3.1.1. --- A General Review of Functionalized Phosphoranoimine Ligands --- p.52Chapter 3.1.2. --- A General Review of Group 14 Metal Complexes Containing Bis(Phosphoranoimines) Ligands --- p.59Chapter 3.2. --- Objective --- p.61Chapter 3.3. --- Results and Discussion --- p.64Chapter 3.3.1. --- Preparation and Characterization of Bis(Phosphoranoimido) Magnesium Complexes --- p.64Chapter 3.3.1.1. --- "Preparation and Characterization of Bis(Phosphoranoimido) Magnesium Complexes [Mg{(Me3SiN=PR2CH)2C5H3N-2,6}THF] (R = Pri, 9; R = Ph, 10)" --- p.64Chapter 3.3.1.2. --- Physical and Spectroscopic Properties of Complexes 9 and 10 --- p.64Chapter 3.3.1.3. --- Molecular Structures of Complexes 9 and 10 --- p.65Chapter 3.3.2. --- Preparation and Characterization of Bis(Phosphoranoimido) Tin(II) and Lead(II) Complexes --- p.70Chapter 3.3.2.1. --- "Preparations and Characterizations of 1,3-Distannacyclobutane with Chlorotin(II) Alkyl Complex [{2-{Sn{C(Pri2P=NSiMe3)}}-6- {Sn{CH(Pri2p=NSiMe3)}Cl}}C5H3N]2 (11) and 1,3-Diplumbacyclobutane with bis(trimethylsilyI)amido Lead(II) Alkyl Complex [{2-{Pb{C(Pri2P=NSiMe3)}}-6-{Pb{CH(Pri2P=NSiMe3)}N(SiMe3)2}}- C5H3N]2 (12)" --- p.70Chapter 3.3.2.2. --- Physical and Spectroscopic Properties of Complexes 11 and 12 --- p.73Chapter 3.3.2.3. --- Molecular Structures of Complexes 11 and 12 --- p.74Chapter 3.3.3. --- Preparation and Characterization of Bis(Phosphoranoimido) Germanium(II) Enamido and Alkyl Complex --- p.79Chapter 3.3.3.1. --- Preparation and Characterization of Bis(Phosphoranoimido) Germanium(II) Enamido and Alkyl Complex [{2-CH(Pri2P=NSiMe3)-6-CH(Pri2P=NSiMe3)}C5H3NGe{2-{C(Pri2P=NSi Me3)Ge} -6-CH2(Pri2P=NSiMe3)} C5H3N] (13) --- p.79Chapter 3.3.3.2. --- Physical and Spectroscopic Properties of Complex 13 --- p.81Chapter 3.3.3.3. --- Molecular Structure of Complex 13 --- p.81Chapter 3.3.4. --- Comparison on Structures and Reactivities of Compounds 11-13 --- p.85Chapter 3.4. --- Experimental Section --- p.87Chapter 3.5. --- References --- p.91APPENDIX IChapter A --- General Experimental Procedures and Physical Measurement --- p.95Chapter B --- X-Ray Crystallography --- p.96APPENDIX IITables of Crystallographic Data and Refinement Parameters --- p.9

Divalent transition metal complexes supported by sterically demanding amido ligands.

by Au Yeung Ho Yu.Thesis (M.Phil.)--Chinese University of Hong Kong, 2006.Includes bibliographical references.Abstracts in English and Chinese.Abstract --- p.i摘要 --- p.iiiAcknowledgement --- p.vTable of Contents --- p.viAbbreviations --- p.ixList of Compounds --- p.xChapter Chapter 1 --- A General Introduction To Late Transition Metal AmidesChapter 1.1 --- General Background --- p.1Chapter 1.2 --- An Overview of Late Transition Metal Amides --- p.2Chapter 1.3 --- Objectives of This Work --- p.7Chapter 1.4 --- References for Chapter1 --- p.9Chapter Chapter 2 --- Late Transition Metal Complexes Derived From 2-Pyridyl Amido LigandChapter 2.1 --- General BackgroundChapter 2.1.1 --- A Brief Introduction to Pyridine-Functionalized Amido Ligands --- p.13Chapter 2.1.2 --- Late Transition Metal Complexes Supported by 2-Pyridyl Amido Ligands --- p.14Chapter 2.2 --- Aims of Our Study --- p.18Chapter 2.3 --- Result and DiscussionChapter 2.3.1 --- Preparation of the [N(CH2But)(2-C5H3N-6-Me)]- Ligand and the Corresponding Lithium Derivatives --- p.19Chapter 2.3.2 --- Syntheses and Structures of Iron(II) and Cobalt(II) AmidesChapter 2.3.2.1 --- "Synthesis of [M(L1)2(HL1)] [M = Fe (6), Co (7)]" --- p.20Chapter 2.3.2.2 --- Physical Characterization of Compounds 6 and7 --- p.24Chapter 2.3.2.3 --- Molecular Structures of Compounds 6 and7 --- p.24Chapter 2.4 --- Experimentals for Chapter 2 --- p.31Chapter 2.5 --- References for Chapter 2 --- p.34Chapter Chapter 3 --- Synthetic and Structural Studies of Late Transition Metal AnilidesChapter 3.1 --- An Overview on Anilido Complexes --- p.40Chapter 3.2 --- Aims of Our Study --- p.45Chapter 3.3 --- Result and DiscussionChapter 3.3.1 --- Aniline Precursors and The Lithium DerivativesChapter 3.3.1.1 --- Syntheses of the Aniline Precusors HLn (n = 2-5) --- p.46Chapter 3.3.1.2 --- Syntheses of Lithium Derivatives of Ln (n = 2-5) --- p.47Chapter 3.3.1.3 --- Physical Characterization of Compounds 11-13 --- p.48Chapter 3.3.1.4 --- "Molecular Structures of Compounds 11a, 12a and 12b" --- p.49Chapter 3.3.2 --- Syntheses and Structures of Late Transition Metal AnilidesChapter 3.3.2.1 --- Syntheses of N-Silylated Anilides --- p.57Chapter 3.3.2.2 --- Physical Characterization of Compounds 14-20 --- p.64Chapter 3.3.2.3 --- Molecular Structures of Compounds 14-20 --- p.65Chapter 3.3.2.4 --- Syntheses of N-Alkylated Anilides --- p.89Chapter 3.3.2.5 --- Physical Characterization of Compounds 21-26 --- p.92Chapter 3.3.2.6 --- "Molecular Structures of Compounds 21, 23, 25 and 26" --- p.93Chapter 3.4 --- Experimentals for Chapter 3 --- p.103Chapter 3.5 --- References for Chapter 3 --- p.112Chapter Chapter 4 --- Reactions of Late Transition Metal Anilides and Their DerivativesChapter 4.1 --- General BackgroundChapter 4.1.1 --- Reactions of Late Transition Metal Amides --- p.124Chapter 4.1.2 --- A Brief Introduction to Oxidative Coupling of Phenols --- p.129Chapter 4.1.3 --- A Brief Overview on the Ring-Opening Polymerization of Cyclic Esters --- p.130Chapter 4.2 --- Aims of Our Study --- p.132Chapter 4.3 --- Results and DiscussionChapter 4.3.1 --- Reactions of Late Transition Metal Anilides and Their DerivativesChapter 4.3.1.1 --- Ligand Substitution --- p.133Chapter 4.3.1.2 --- Chloride Abstraction --- p.137Chapter 4.3.1.3 --- Chemical Reduction --- p.138Chapter 4.3.1.4 --- Reaction with Unsaturated Compounds --- p.139Chapter 4.3.1.5 --- Physical Characterization of Compounds 27-33 --- p.140Chapter 4.3.1.6 --- Molecular Structures of Compounds 27-33 --- p.142Chapter 4.3.2 --- Oxidation of Bisaryloxide Complexes --- p.162Chapter 4.3.3 --- The Ring-Opening Polymerization of e-Caprolactone --- p.167Chapter 4.4 --- Experimentals for Chapter 4 --- p.171Chapter 4.5 --- References for Chapter 4 --- p.176"Appendix 1 General Procedures, Physical Measurements and X-Ray Structure Analysis" --- p.187Appendix 2 NMR Spectra of Compounds --- p.189Appendix 3 Selected Crystallographic Data --- p.20

Towards terminal rare earth imido complexes

The development of rare earth complexes supported by a bisphosphinimine pyrrole-based pincer ligands is described herein. Synthesis of these species was conducted via alkane elimination and salt metathesis pathways. These complexes and their precursors were prepared and characterized by multi-dimensional (1-, pseudo-2-, and 2-dimensional), multi-nuclear (1H, 2H, 11B, 13C, 19F, and 31P) NMR spectroscopy, single-crystal X-ray diffraction analysis and elemental analysis. Systematic modifications to the ancillary ligand and the resulting impact on complex reactivity is also presented with the ultimate goal of generating a species that bears a rare earth-nitrogen double bond. Specifically, electron withdrawing (Ph) and donating (iPr) groups were installed on the phosphinimine P atoms of the ligand and Pipp (4-iPrC6H4) and Pm (4,6-dimethylpyrimidine) were utilized on the phosphinimine nitrogen atoms. Each iteration of the ancillary ligand led to distinct and unique reactivities upon complexation to a rare earth metal