Synthetic, Structural and Computational Studies on Heavier Tetragen and Chalcogen Triazenide Complexes

The syntheses of the triazenide complexes [{N(N Dipp) 2} 2M] (Dipp = 2,6-di-isopropylphenyl; M = Ge(II) (1), Sn(II) (2), Pb(II) (3), and Te(II) (5)) are described for the first time. These compounds have been characterized by single-crystal X-ray diffraction and heteronuclear NMR spectroscopy. Density functional theory calculations were employed to confirm the presence and nature of the stereochemically active lone pairs in 1-5, alongside the Gibbs energy changes for their general synthesis, which enable the rationalization of observed reactivities. </p

Organoiridium complexes : anticancer agents and catalysts

Iridium is a relatively rare precious heavy metal, only slightly less dense than osmium. Researchers have long recognized the catalytic properties of square-planar Ir(I) complexes, such as Crabtree's hydrogenation catalyst, an organometallic complex with cyclooctadiene, phosphane, and pyridine ligands. More recently, chemists have developed half-sandwich pseudo-octahedral pentamethylcyclopentadienyl Ir(III) complexes containing diamine ligands that efficiently catalyze transfer hydrogenation reactions of ketones and aldehydes in water using H2 or formate as the hydrogen source. Although sometimes assumed to be chemically inert, the reactivity of low-spin 5d(6) Ir(III) centers is highly dependent on the set of ligands. Cp* complexes with strong σ-donor C^C-chelating ligands can even stabilize Ir(IV) and catalyze the oxidation of water. In comparison with well developed Ir catalysts, Ir-based pharmaceuticals are still in their infancy. In this Account, we review recent developments in organoiridium complexes as both catalysts and anticancer agents. Initial studies of anticancer activity with organoiridium complexes focused on square-planar Ir(I) complexes because of their structural and electronic similarity to Pt(II) anticancer complexes such as cisplatin. Recently, researchers have studied half-sandwich Ir(III) anticancer complexes. These complexes with the formula [(Cp(x))Ir(L^L')Z](0/n+) (with Cp* or extended Cp* and L^L' = chelated C^N or N^N ligands) have a much greater potency (nanomolar) toward a range of cancer cells (especially leukemia, colon cancer, breast cancer, prostate cancer, and melanoma) than cisplatin. Their mechanism of action may involve both an attack on DNA and a perturbation of the redox status of cells. Some of these complexes can form Ir(III)-hydride complexes using coenzyme NAD(P)H as a source of hydride to catalyze the generation of H2 or the reduction of quinones to semiquinones. Intriguingly, relatively unreactive organoiridium complexes containing an imine as a monodentate ligand have prooxidant activity, which appears to involve catalytic hydride transfer to oxygen and the generation of hydrogen peroxide in cells. In addition, researchers have designed inert Ir(III) complexes as potent kinase inhibitors. Octahedral cyclometalated Ir(III) complexes not only serve as cell imaging agents, but can also inhibit tumor necrosis factor α, promote DNA oxidation, generate singlet oxygen when photoactivated, and exhibit good anticancer activity. Although relatively unexplored, organoiridium chemistry offers unique features that researchers can exploit to generate novel diagnostic agents and drugs with new mechanisms of action

Synthetic Applications of Polar Transition Metal Metallocenes

Since the sandwich structure of ferrocene was elucidated in 1952, metallocenes have generated a vast amount of interest. Transition metal metallocenes have previously been shown to be suitable precursors in the syntheses of novel organometallic and metallo-organic complexes, although the use of metal halide starting materials for organometallic synthesis is much more common due to their being readily commercially available and generally easier to handle than the extremely air- and moisture-sensitive metallocene alternatives. In this project, the polar transition metal metallocenes Cp2V, Cp2Cr, Cp2Mn and Cp2Ni were employed as precursors in the synthesis of fourteen novel metal containing complexes, in several cases generating products which could not have been obtained using metal halide starting materials.EPSR

Tailor made mixed-metal reagents for metalation/C-C bond forming processes

The thesis focusses on advancing the understanding on cooperative effects heterobimetallic compounds which combine an alkali-metal with a divalent metal such as magnesium, zinc and manganese. Through rational design, several alkali-metal ates have been prepared and structurally authenticated. Their applications towards two fundamental organic transformations, namely, deprotonative metallation and metal-halogen exchange have been investigated. Chapter 2 discloses a new family of sodium zincates containing the bulky chelating silyl(bis) amide {Ph2Si(NAr*)2}2¯ (Ar*= 2,6-diisopropylphenyl). Illustrating the enhanced kinetic basicity of Zn-N bonds versus Zn-C bonds, reacting Ph2Si(NHAr*)2 (1) with an equimolar mixture of NaCH2SiMe3 and Zn(HMDS)2 (HMDS= N(SiMe3)2) furnished alkyl sodium zincate [{(Ph2Si(NAr*)2)Zn(CH2SiMe3)}¯{Na(THF)6}+] (3). Contrastingly using a stepwise approach, by treating 1 first with NaCH2SiMe3 afforded sodium amide [{Ph2Si(NHAr*)(NAr*)Na}2] (5), which can subsequently undergo co-complexation with Zn(HMDS)2, favouring the metallation of the remaining NHAr* group to give heteroleptic tris(amido) zincate [{(Ph2Si(NAr*)2)Zn(HMDS)}¯{Na(THF)6}+] (6). The reactivity of sodium zincates 6, 3 and [NaZn(CH2SiMe3)3] (4) towards 2,4,6-trimethylacetophenone led to the isolation of enolate complexes [{(THF)NaZn(OC(=CH2)Mes)3}2] (9), [{(THF)NaZn(CH2SiMe3)(OC(=CH2)Mes)2}2] (8), and [{(THF)Na(OC(=CH2)Mes)}4] (10) (Mes= 2,4,6 trimethylphenyl), respectively. These studies revealed that the chelating silyl(bis)amide {Ph2Si(NAr*)2}2− far from being an innocent spectator is an effective base for the deprotonation of this ketone, showing an unexpected superior kinetic basicity than the CH2SiMe3 alkyl group when part of sodium heteroleptic zincate 3. The bimetallic constitution of enolates 9 and 8 contrasts with that of all-sodium 10, which is formed with concomitant elimination of Zn(CH2SiMe3)2. Revealing the divergent behaviour of Mg versus Zn in these bimetallic systems, reaction of 2,4,6-trimethylacetophenone with the magnesium analogue of 3, [{Ph2Si(NAr*)2Mg(CH2SiMe3)}−{Na(THF)6}+] (11), produces magnesiate enolate [{Ph2Si(NAr*)2Mg(O(=CH2)Mes)(THF)}−{Na(THF)5}+] (12), where the chelating silyl(bis)amide ligand is retained and metalation of the ketone is actioned by the alkyl group. Chapter 3 exploits the sequential deprotonative co-complexation approach developed in Chapter 2 to access novel potassium metal(ates). Thus, monometallation of 1 is accomplished using potassium alkyl KCH2SiMe3 yielding [{Ph2Si(NHAr*)(NAr*)K}∞] (13), which, in turn, undergoes co-complexation with the relevant M(CH2SiMe3)2 (M=Mg, Zn, Mn) enabling metallation of the remaining NHAr* group to furnish silylbis(amido) alkyl potassium metal(ates) [{Ph2Si(NAr*)2M(THF)x(CH2SiMe3)}−{K(THF)y}+] (M=Zn, x=0, y=4, 14; M=Mg, x=1, y=3, 15; and M=Mn, x=0, y=4, 16). Reactivity studies of potassium manganate 16 with the amine HMDS(H) revealed the kinetic activation of the remaining alkyl group on Mn furnishing [K(THF)2{Ph2Si(NAr*)2}Mn(HMDS)] (18). Similarly 16 reacts with phenyl acetylene to give [{Ph2Si(NAr*)2Mn(THF)(C≡CPh)}¯{K(THF)3}+] (17). The structures of these bimetallic complexes along with that of the potassium precursor 13 have been established by X-ray crystallographic studies. Chapter 4 introduces a new type of heterobimetallic base, the specially designed potassium zincate [{Ph2Si(NAr*)2Zn(TMP)}¯{K(THF)6+] (19) which combines a sterically demanding silyl(bis)amide ligand with a kinetically activated terminal TMP amide group (TMP= 2,2,6,6-tetramethylpiperidide). Circumventing common limitations of conventional s-block metallating bases, 19 enables efficient and regioselective zincation of a broad range of substituted fluoroarenes including hypersensitive fluoronitrobenzene derivatives. Trapping and characterization of the organometallic species involved in these reactions [{Ph2Si(NAr*)2Zn(ArF)}¯{K(THF)x+] (ArF =C6H2F3, C6H3F2, C6H2Cl3, C6H2F2NO2, C6H3FNO2, C11H6F2N, C5H3FN, C6F5, C6HF4 and C6F4; x= 3-6) has provided informative mechanistic insights on how these direct zincation reactions may occur as well as shed light on the key role of the supporting silyl(bis)amido ligand. The first examples of directly metalated nitroarenes to be structurally characterised have been presented as well as the ability of this approach to promote polyzincations of fluoroarenes has been disclosed. Expanding the synthetic potential of this heterobimetallic approach it has been shown that these organometallic compounds can engage in onward C-C bond forming processes. Chapter 5 explores the synthesis and reactivity of higher order manganates [(TMEDA)2AM2Mn(CH2SiMe3)4] (AM= Li, 37; Na, 43; K; TMEDA= N,N,N’,N’-tetramethylethylenediamine) to promote Mn-I exchange /alkyne metallation reactions in tandem with oxidative homocoupling reactions. Lithium manganate 37 enables the efficient direct Mn–I exchange of aryliodides, affording transient (aryl)lithium manganate intermediates which in turn undergo spontaneous C−C homocoupling at room temperature to furnish symmetrical (bis)aryls in good yields under mild reaction conditions. The combination of EPR with X-ray crystallographic studies has revealed the mixed Li/Mn constitution of the organometallic intermediates involved in these reactions, including the homocoupling step which had previously been thought to occur via a single-metal Mn aryl species. These studies show Li and Mn working together in a synergistic manner to facilitate both the Mn–I exchange and the C−C bond-forming steps. Both steps are carefully synchronized, with the concomitant generation of the alkyliodide ICH2SiMe3 during the Mn–I exchange being essential to the aryl homocoupling process, wherein it serves as an in situ generated oxidant. Sodium manganate 43 reacts with 4 equivalents of phenylacetylene to give [(THF)4Na4Mn2(C≡CPh)8] (45) which when exposed to dry air furnishes the relevant 1,3 enyne in a 97% yield

Reactivity of a Low Valent Gallium Compound

The work described in this thesis is conducted to expand the reactivity of the β-diketiminate gallium(I) compound, NacNacGa (NacNac=[ArNC(Me)HC(Me)NAr]−, Ar=2,6-iPr2C6H3). The reactivity of NacNacGa towards various unsaturated compounds is studied. In particular, reaction between NacNacGa and phenyl isothiocyanate resulted in the oxidative addition of the C=S bond under ambient conditions, leading to the isolation cyclization product NacNacGa(κ2-S2CNPh) and sulfide isocyanide-bridged dimer (NacNacGa)2(μ-S)(μ-CNPh). Additionally, a [1+4] cycloaddition with a conjugated aldehyde (methacrolein) and a [1+2+3] cycloaddition with isocyanate and carbodiimide are presented. The oxidative cleavage of P=S bond of triphenylphosphine sulfide at increased temperatures gave the previously reported sulfide bridged gallium dimer. In situ oxidation of NacNacGa in the presence of substrates featuring donor sites led to the C-H activation reactions. As such, C-activation of pyridine N-oxide, pyridine, cyclohexanone, DMSO, and Et3P=O by a transient NacNacGa=O resulting in the corresponding gallium hydroxides is demonstrated. DFT calculations suggested initial formation of adducts between substrates and NacNacGa=O followed by a C-H bond abstraction from the substrate. Similarly, a transient gallium imide NacNacGa=NSiMe3, generated from the reaction of NacNacGa with trimethylsilyl azide, is shown to cleave C-H bonds of pyridine, cyclohexanone, ethyl acetate, DMSO, and Et3P=O with the formation of gallium amides. In an attempt to isolate a gallium alkylidene, NacNacGa was treated with trimethylsilyl(diazomethane). Instead, a monomeric gallium nitrilimine and a metalated diazomethane were obtained. The gallium nitrilimine undergoes 1,3-addition reaction with phenylsilane and catecholborane forming gallium hydrazonides. Its reaction with diborane resulted in the formal nitrene insertion into the B-B bond to produce a gallium diborylamide. DFT calculations revealed intermediate gallium alkylidene formation from the reaction of NacNacGa with diazomethane that upon reaction with the second equivalent of diazomethane leads to a gallium nitrilimine

Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis

Bismuth has recently been shown to be able to maneuver between different oxidation states, enabling access to unique redox cycles that can be harnessed in the context of organic synthesis. Indeed, various catalytic Bi redox platforms have been discovered and revealed emerging opportunities in the field of main group redox catalysis. The goal of this perspective is to provide an overview of the synthetic methodologies that have been developed to date, which capitalize on the Bi redox cycling. Recent catalytic methods via low-valent Bi(II)/Bi(III), Bi(I)/Bi(III), and high-valent Bi(III)/Bi(V) redox couples are covered as well as their underlying mechanisms and key intermediates. In addition, we illustrate different design strategies stabilizing low-valent and high-valent bismuth species, and highlight the characteristic reactivity of bismuth complexes, compared to the lighter p-block and d-block elements. Although it is not redox catalysis in nature, we also discuss a recent example of non-Lewis acid, redox-neutral Bi(III) catalysis proceeding through catalytic organometallic steps. We close by discussing opportunities and future directions in this emerging field of catalysis. We hope that this Perspective will provide synthetic chemists with guiding principles for the future development of catalytic transformations employing bismuth

Porphyrin-silica gel hybrids as effective and selective copper(II) adsorbents from industrial wastewater

Porphyrins are an important class of ligands with a tremendous ability to capture metal ions closely related to the rich coordination chemistry of porphyrins. Herein we use this characteristic to develop silica gel grafted derivatives for water remediation applications. Therefore, two porphyrin derivatives, one with three and the other with four mercaptopyridyl units were grafted on silica gel functionalized with 3-aminopropyltriethoxysilane. The new adsorbents Si3PyS and Si4PyS were characterized using a suitable set of techniques confirming the covalent attachment of the porphyrins to the silica surface. Additionally, microscopy and N2 adsorption analysis confirmed the structural integrity and preservation of the mesoporous structure of Si during surface modification. The results show that both hybrid materials exhibit good chemical and thermal stability and an outstanding Cu2+ removal capability, with a chemical adsorption capacity of 176.32 mg g–1 and 184.16 mg g–1, respectively. These materials have also been used in real water and industrial wastewater samples with minimal interference in their adsorption capabilities. Density Functional Theory calculations were performed to confirm the good performance of the hybrid materials Si3PyS and Si4PyS towards metal ions. The functionalization of silica surface with porphyrin-based ligands bearing additional binding motifs drastically improves the adsorption capability of the new hybrids towards metal ions. The presence of pyridyl units brings a meaningful advantage, since both porphyrin core and appended pyridyl groups are able of binding Cu2+ ions with high affinity, contributing to the enhancement of the chelating features of the adsorbents prepared when compared with other ligands supported in silica-based materials.publishe

Synthesis and Reactivity of Main Group Complexes for Applications in Small Molecule Activation

The work described in this thesis is focused on the preparation of a series of novel main group complexes, featuring unusual structural and bonding situations, and the study of their reactivity toward small molecules. The new zinc complexes dimphZnBu (V-2) and dimphZnCl2Li(THF)3 (V-3), supported by a diiminophenyl (dimph) ligand were prepared. The reaction of complex V-3 with LiHBEt3 resulted in hydride transfer to the C=N imine group to give an unusual zinc dimer (V-7). The latter transformation occurs via formation of compound (ɳ1(C),ĸ1(N)- 2,6-(2,6-iPr2C6H3N=CH)2C6H3)2Zn (V-5) which can be also accessed by reduction of V-7 with KC8. Diiminophenyl (dimph) proved to be an excellent ligand platform to stabilise a low-valent phosphorus centre. The resultant compound dimphP (VI-2), which can be rationalised as an imino-stabilised phosphinidene or benzoazaphopshole, shows remarkable chemical stability toward water and oxygen. VI-2 reacts with excess strong acid HCl to generate the P(III) chloride (dimHph)PCl (VI-6). Surprisingly, substitution of the chloride under some nucleophilic (KOBut) and electrophilic conditions (Me3SiOTf) regenerates the parent compound VI-2 by proton removal from the weakly acidic CH2N position. A related species (dimH2ph)P (VI-10) is produced upon thermal rearrangement of the hydride (dimHph)PH (VI-9). The molecular structure and reactivity of compounds VI-2 and other related compounds are also discussed. The reduction of the O,C,O-chelated phosphorus (III) chloride (VI-16) ( O,C,O = 2,6-bis[(2,6-diisopropyl)phenoxyl]phenyl) with KC8 or PMe3 resulted in the formation of a cyclic three-membered phosphorus compound (VI-18). The intermediacy of phosphinidene VI-17 was confirmed by trapping experiments and a VT 31P{1H} NMR study. The reaction of in-situ generated phosphinidene with either PhSiH3 or HBpin resulted in the formation of an unprecedented phosphine (VI-23). The treatment of VI-16 with two equivalents of DippNHC carbene led to ArP(Cl)NHC product (VI-24). The germylone dimNHCGe (dimNHC = diimino N-Heterocyclic Carbene, VII-8) was successfully prepared by the reduction of germanium cation (VII-7) with KC8. The molecular structure of VII-8 was unambiguously established, using NMR spectroscopy and single-crystal X-ray diffraction analysis. The reactivity of VII-8 was investigated. VII-8 is inactive towards butadiene but undergoes an oxidative cyclization with tetrachloro-o-benzoquinone to give a tetragermanium derivative. VII-8 undergoes oxidation addition of CH3I and PhI, followed by an unusual migration of the Me and Ph groups from germanium to the carbene ligand. Related chemistry takes place upon protonation with dry HCl, which results in the migration of the hydride to the carbene ligand

Syntheses and structural characterisations of amidinates, diaminates and phenolates antimony (I and III) and aluminium (III) complexes

This thesis focuses on the synthesis and characterisation of antimony(III) and aluminium(III) amidates with an emphasis on structural characterisation, presenting the isolation of 22 new complexes. In addition, some chemistry of (2,6-di–tert-butyl-4-methyl) antimony and aluminium (III) complexes is added in the appendix of this thesis. Below is a general outline for each chapter of original research (2-4), showing the diverse range of compounds obtained from the following formamidinate and polyfluorophenylamidate ligands. Chapter 1 gives an overall introduction to antimony and aluminium (III) chemistry. This chapter describes the general aspects and overview of the relevant literature highlighting the most common synthetic methods used to synthesis antimony and aluminium compounds, particularly formamidinates, amidates, phenolates and their applications. Chapter 2 describes the metathesis reactions employed for the preparation of a range of mono- and bis-substituted formamidinato antimony (III) complexes. The bissubstituted complexes include [Sb(DippForm)₂Cl] (2.2), [Sb(DippForm)₂Br] (2.3) and [Sb(DippForm)₂I] (2.4) and mono-substituted products include [Sb(DippForm)Br₂] (2.5) and [Sb(DippForm)I₂] (2.6). Other complexes have been prepared as dimers [Sb(DippForm)(NSiMe₃)]₂ (2.8) and [Sb(DippForm)Cl(C₆F₅)]₂.(THF)₂ (2.12), also the formamidinato-bridged distibane [Sb₂{μ-(DippForm}₂].(THF)₈ (2.1) that represents an example of monovalent antimony. Fundamentally, the synthesis of antimony (I) and (III) formamidinate complexes was accomplished through deprotonation of N,N'-2,6-diisopropylphenylformamidine (DippFormH) by a metal alkyl/amide reagent (n-BuLi, LiN(SiMe₃)₂, NaN(SiMe₃)₂) in a donor solvent THF or in PhMe and then combined with SbX₃ in THF and/or PhMe. The unexpected [(DippForm)ClSb(μ-O)SbCl₂(Me₂NC₂H₄NMe₂)]₂.(C₆D₆) (2.11) was the only type of halogenated hetero dinuclear complex isolated in this study. Chapter 3 details the synthesis and characterisation of a series of heteroleptic and homoleptic N,N-dimethyl-N'-2,3,5,6-tetrafluorophenylethane-1,2-diaminate antimony (III) complexes. [Sb(p-HC₆F₄NC₂H₄NMe₂)₂Cl] (3.2) and [Sb(p-HC₆F₄NC₂H₄NMe₂)3] (3.3) complexes were isolated by metathesis reactions between SbCl3 and Li(p-HC₆F₄N(CH₂)₂NMe₂), a common synthetic route to antimony complexes; while the direct reaction between SbCl3 and p-HC₆F₄NH(CH₂)₂NMe₂ was used to synthesise [Sb(p-HC₆F₄NC₂H₄NMe₂)Cl₂] (3.1). Halo- and nonhalo-polyfluorophenylamido antimony (III) complexes were gained as monomers in the solid state. Chapter 4 Extending this chemistry to formamidinate aluminium resulted in the isolation of a group of new and interesting formamidinato aluminium (III) complexes ranging from mono- to bis-substituted, involving different bonding modes. Metathesis reactions between AlX₃ (X = Cl, Br, I) and two different deprotonated N,N'-chelating ligands (XylForm) and (DippForm) of varying steric bulk and functionality were used to increase the range of the haloorgano(formamidinato) aluminium (III) system. These complexes are [Al(XylForm)₂Cl] (4.1), [Al(XylForm)₂I].PhMe (4.2), [Al(XylFormH)Br₃] (4.3), [Al(DippFormH)Br₃] (4.5) and [Al(DippForm)₂Cl] (4.8). Using the bulkier formamidinate ligand (DippForm) allowed the isolation of [Al(DippForm)Cl₂(thf)] (4.6) and [Al(DippForm)ClBr(thf)] (4.7). The heteroleptic [Al₃(XylForm)₂(μ₃-O)(OH)Cl₄]₂.PhMe (4.4) was isolated as a monomer and represents a compound contained three aluminium atoms bridged by an oxygen atom. In a different approach, a chlorine/methyl exchange reaction was used for forming bimetallic Al/Sb (III) ionic complexes [Me₃Sb-SbMe₂][AlCl₄] (4.9) and [Br₃Sb-μBr-SbBr₃][AlCl₂(thf)₄] (4.10), showing relatively rare coordination modes. Overall, the knowledge regarding amidato antimony and aluminium (III) complexes has been enhanced and more information has been obtained regarding their structural motifs and bonding modes. The N,N'-bis(aryl)formamidinate ligands can form stable and structurally interesting mono/trivalent antimony and trivalent aluminium species using metathesis route, due to their ease of steric variability. In addition, this thesis demonstrates the ability of N,N-dimethyl-N'-2,3,5,6-tetrafluorophenylethane-1,2-diaminate ligand to stabilise antimony in its most common and stable oxidation state (III). Many of these compounds, particularly the compounds with M-X bonds, are now well set for potential reduction to low valent species. Reaction with KC₈ should form isolable low valent Sb or Al complexes and this work could be performed in future work. There are also many other formamidinate, guanidinate and amidinate ligands that could be used to extend this work

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