The chemistry of metal–metal (M–M) multiply bonded compounds has fascinated inorganic chemists for a period spanning more than five decades. Since the elucidation of the quadruple bond by Cotton in 1964, thousands of compounds featuring M–M bonds have been isolated and studied. Of these, dinuclear units supported by four bidentate ligands forming a ‘paddlewheel’ motif represent a class of compounds that present unique molecular and electronic structures, and useful electrochemical and magnetic properties.<div><br></div><div>Over the last two and a half decades, our laboratory has focused on studying diruthenium paddlewheel complexes for their easeof preparation, rich electrochemical properties,and remarkable stability. We have isolated a vast number of diverse diruthenium alkynyls in multiple oxidation states, bearing different paddlewheel (equatorial) ligand systems and studied their molecular and electronic structures. Taking advantage of the extended conjugation that exists between the Ru2core and the poly-alkynyl ligand motif, we have also found applications for them in prototypical flash-memory devices. At this juncture, we sought to expand the organometallic chemistry of Ru2to complexes featuring Ru–aryl linkages.<br></div><div><br></div><div>The ‘aryl anion’ is, based on pKa, twenty orders of magnitude more basic than the corresponding acetylide. Arguably, this difference should result in a more electron-rich dinuclear core with new electronic structures waiting to be explored. Although kinetically more reactive than metal–alkynyls, metal–aryls are still more stable than the corresponding metal–alkyls. However, for second-row transition metals like ruthenium, kinetic instability issues are somewhat more suppressed than for their first-row counterparts.<br></div><div><br></div><div>Armed with the knowledge that it was reasonable to expect somewhat stable metal–aryl complexes, the synthesis and characterization, and analyses of molecular and electronic structures of diruthenium aryls were attempted. By employing relatively simple lithium-halogen exchange reactions, both mono and bis-aryl complexes of diruthenium have been isolated. Additionally, two different oxidation states of diruthenium have beenaccessed, namely Ru2(II,III)and Ru2(III,III),by judiciously modifying the paddlewheel ligands. Following this, preliminary reactivity studies of Ru2(II,III) monoaryls of the form Ru2(ap)4Ar were performed, which yielded surprising results. This work led to the conclusion that the diruthenium–aryl interaction is an example of a metal–metal–ligand interaction that can bring reactivity to the distal metal site. Moreover, it was found that even minor changes in axial ligands can bring about major upheavals in electronic structure.<br></div><div><br></div><div>Computational investigations into the electronic structure of the above-mentioned compounds have faced many a barrier because of the complexity of the system. The deep mixing of the metal–metal and metal–ligand valence manifolds is more easily isolated into its constituent parts in the case of relatively simple structures such as the monoaryls, Ru2II,IIIL4Ar. However, electronic structure calculations are fraught with difficulties in the case of heavily distorted axially disubstituted mono and bis-aryls, (X)Ru2III,IIIL4Ar and Ru2III,IIIL4Ar2, respectively. Ru2III,IIIL4Ar2complexes present an interesting case of second order Jahn-Teller distortion (SOJT), which has been adequately modeled. However, the more heavily distorted case of XRu2(ap)4Ar (X = CCH, CN, CO, etc.) pose greater computational challenges, such as low-lying excited states, spin-admixed ground states and difficulties in isolating metal and ligand contributions to the valence manifold. <br></div><div><br></div><div>Our investigations into diruthenium aryls began as a mere curiosity that arose out of a serendipitous discovery. Two years later, our continued efforts in this direction have yielded rather fruitful results. The unusual structures and associated complex bonding motifs in these systems have taught us about the importance of metal–metal–ligand interactions as more than just a sum of metal–metal and metal–ligand parts.<br></div>

Paddlewheel complexes are molecules in which two interacting metal atoms are bridged by four chelating ligands. This class of complexes has a large range of electronic variability while keeping a rigid geometric structure. This variability has led to their use as catalysts, strong reductants, anti-tumor agents, and electron transfer agents. This dissertation examines the effects of changing both the dimetal core and the surrounding ligands on the electronic structure properties of the paddlewheel complexes. Examination of Bi₂(O₂CCF₃)₄, a p-orbital dimetal paddlewheel complex, provided a way to probe the orbitals that are important in metal-ligand σ bonding. The b(1g) and b(2u) ligand orbitals of Bi₂(O₂CCF₃)₄ have no dimetal orbital counterpart, unlike the case of the more familiar d-orbital dimetal paddlewheel complexes such as Mo₂(O₂CCF₃)₄. This had the effect of destabilizing these ligand orbitals compared to d-orbital paddlewheel complexes. The ligand a1g orbital in Bi₂(O₂CCF₃)₄ was also destabilized due to nodal differences in the dimetal σ orbital. The unusual coincidence of Mo-Mo σ and π ionization bands is due to a greater amount of ligand character in the Mo-Mo σ orbital compared to its ditungsten analogue, which has separate ionization bands for the σ and π bonds. A series of p-substituted dimolybdenum tetrabenzoate complexes was synthesized and studied by photoelectron spectroscopy in order to further examine the delocalization of electron density from the metals to the ligands in these complexes. A 0.89 eV shift in the δ ionization band was observed from Mo₂(O₂CPh-p-OMe) ₄ and Mo₂(O₂CPh-p-CF₃)₄. Overlap effects are the major factor causing the shift in the δ bond ionization, as the calculated charges on the molybdenum and oxygen atoms did not vary significantly on change of substituent. Molybdenum and tungsten guanidinate paddlewheel complexes have promise as good reducing agents due to their extremely low ionization energies. The solubility of the complexes poses a problem for their widespread adoption for use as reducing agents. Alkyl substituents were added to the complexes to increase their solubility. W₂(TEhpp)₄ was observed to have the lowest ionization energy at 3.71 eV (vertical ionization) and 3.40 eV (onset ionization) of any molecule yet prepared.

Spray forming with eo-injection of a solid particulate phase to form a metal-metal composite has been studied as a new route for manufacture. Two Al-based matrices were investigated: AI-12Si for testing the feasibility of the new manufacturing route and Al-4Cu for providing better mechanical performance. For both composite types, Ti was chosen as the particulate phase and the processing-microstructure-property relationships then studied. At Peak Werkstoff GmbH, Germany 12 wt%Ti particles were eo-injected into an atomised Al alloy droplet spray and eo-deposited to form a rv300 kg billet. The microstructure comprised refined equiaxed a-AI grains (rv5fLm), spherical Si particles (rv5fLm) and uniformly distributed Ti particles (rv80fLm). Sections of the billet were extruded under a range of conditions into long strips 20mm wide and 6mm, 2.5mm and 1mm thickness. At high strains, the Ti particles were deformed into continuous fibres of a few microns in thickness. Accumulative roll bonding was then performed to higher total strains, while maintaining a constant cross-section, reducing the Ti fibres to sub-micron thickness. The fibres were studied by extraction after selective dissolution of the a-AI matrix. There was no interfacial reaction between a-AI and Ti or any measurable oxide formation, thus providing encouragement for the manufacture of metal-metal composites by eo-spray forming. A powder injection pump was successfully integrated and commissioned on the spray forming facility at Oxford University. The pump was calibrated to optimise powder flow rates. Three AI-4Cu+ Ti composite billets were processed with each containing Ti powder with a different processing history. Up to 20vol%Ti was successfully incorporated, however due to the cooling effect from powder injection, porosity was significant. The quenching effect provided a finer AI-4Cu grain structure in the region of Ti injection, and also promoted precipitation of O'-AbCu precipitates. A Ti/ Al-4Cu interfacial reaction was more prominent in the billet spray formed at 850°C than those spray formed at 750°C. Angular Ti processed by a hydride-dehydride route had better deformation characteristics than spherical gas atomised Ti. Deformation processing by extrusion and rolling was investigated for Al-4Cu+20vol%Ti using SEM, EBSD and FIB. After extrusion to a strain of 5, the composite contained elongated reinforcing fibres characteristic of metal-metal composites. The microstructure studied by EBSD revealed equiaxed polygonal Al-4Cu matrix grains. Rolling was not as efficient as extrusion in producing elongated Ti fibres and was attributed to a lower deformation processing temperature. The rolled composites consisted of elongated Al-4Cu grains 1-5J1m in thickness. An UTS of 339MPa at a strain of 3 was attributed to texture strengthening in the Q- AI.

by Mok-Yin Chow. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1992. / Includes bibliographical references (leaves 55-58). / Acknowledgement --- p.1 / Abstract --- p.2 / Contents --- p.3 / List of Figures --- p.4 / List of Tables --- p.5 / Chapter 1. --- Introduction --- p.6 / Chapter I. --- Chemistry of pseudohalides --- p.6 / Chapter II. --- Infrared spectroscopy of pseudohalides --- p.8 / Chapter III. --- Chemistry of metal carboxylates --- p.10 / Chapter IV. --- Infrared spectroscopy of carboxylates --- p.13 / Chapter V. --- Chemistry of betaine ligands --- p.14 / Chapter VI. --- Objectives of this research --- p.15 / Chapter 2. --- Experimental --- p.17 / Chapter I. --- Preparation --- p.17 / Chapter II. --- X-ray crystallography --- p.21 / Chapter 3. --- Results and discussion --- p.23 / Chapter I. --- "Isostructural complexes Co2(bet)2(N3)4 1,Zn2(bet)2(N3)42, Cd2(bet)2(N3)4 3, and Cd2(bet)2(NCO)4 4" --- p.23 / Chapter II. --- Copper(II) complex Cu2(bet)2(N3)2(N03)2 5 --- p.29 / Chapter III. --- Cadmium(II) complexes Cd3(bet)4(SCN)6(H20)2 6 and Cd(prbet)(NCS)2 7 --- p.34 / Chapter IV. --- Barium(II) complex Ba(pybet)2(NCS)2 8 --- p.43 / Chapter V. --- Cobalt(II) complex [Co(pybet)2(NCS)(H20)3]2[Co(NCS)4] 9 --- p.49 / Chapter VI. --- Conclusion --- p.53 / References --- p.55 / Publications based on work reported in this thesis --- p.59 / Appendix --- p.60

by Maoqi Feng. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2000. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

by Shan-Ming Kuang. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (p. 135-152). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web.

The syntheses of a new class of polycyclic TriAmino DiCarbenes (TADCs), based on 3,9-diazajulolidine, and their precursors and adducts are described. Starting with 2,6-dimethyl-nitrobenzene, 2,6-bis ((alkylamino)methyl)anilines (alkyl = isopropyl, mesityl, and tert-butyl) were synthesized in 40% yield over five steps. These triamines were then di-cyclized stepwise to diformamidinium dications or formamidinium/2-methoxyformaminals using oxonium salts and trialkyl orthoformates. A diformamidinium dication was characterized by single-crystal X-ray diffractometry. Treatment with various bases, particularly lithium hexamethyldisilylazide, led to the novel TADCs and monocarbenes, two of which were isolated and characterized by 1H and 13C NMR spectroscopies. In both cases, treatment with elemental sulfur trapped the TADCs as dithiobiurets. No TADC-transition metal complexes were successfully isolated from reactions of the diformamidinium dications or LiHMDS TADC complex with a number of transition metal complexes. With the exception of these two cases, all other TADCs were not isolated because they rapidly reacted to form dimers, trimers, and tetramers. One of these dimers was isolated and its structure determined using 1D and 2D NMR spectroscopies, along with high-resolution electrospray ionization mass spectrometry. This revealed that the TADC had dimerized to form an ene-triamine, likely via 1,3-shift of a benzylic proton. Novel N-heterocyclic Carbene (NHC) complexes of molybdenum were also synthesized and characterized. Reaction of Cp2Mo2(CO)4 (Cp = C5H5) with dimesityl-imidazol-2-ylidenes (IMes) or dimesityl-imidazolidin-2-ylidenes (SIMes) yielded the molybdoradicals CpMo(CO)2(NHC) (NHC = IMes or SIMes). The carbonyl infrared stretching frequencies and the relative metal-to-NHC π-backbonding for IMes and SIMes complexes are compared. Reaction of the less bulky dimethyl-imidazol-2-ylidene (IMe) with Cp2Mo2(CO)4 yielded the Mo-Mo triple bond complex Cp2Mo2(CO)3(IMe) by CO substitution. This is the first example of an NHC-ligated metal-metal multiply bonded complex. Single crystal X-ray diffractometry of these new organomolybdenum and organodimolybdenum complexes is discussed.

A series of dimolybdenum compounds having a Mo2 4+ core coordinated by various ligands, including formamidinate (e.g. DAniF = N, NN-di-p-ansisylformamidinate ), acetate and/or acetonitrile molecules, have been synthesized as building blocks for the construction of Mo2-containing supramolecular arrays. Compound Mo2(DAniF)3(O2CCH3) was specifically designed for the preparation of dimolybdenum pairs, whereas the others meet the needs of Mo2 4+ units for different geometry settings. Compounds described by a general formula [Mo2]L[Mo2], where [Mo2] = [Mo2(DAniF)3]+, have two dimetal units electronically coupled by the central unit L , which consequently engender significant impact on the redox property and electronic structure of the molecule. It is found that in the weakly coupled complex system, [Mo2]M(OCH3)4[Mo2] (M = Zn and Co), the mixed-valence complexes present asymmetric molecular structures with two distinct [Mo2] units corresponding to be a bond order 4.0 (F2B4*2) and 3.5 (F2B4*1), respectively. EPR and magnetic susceptibility measurements for the doubly oxidized species show that there is no significant antifferromagnetic spin coupling. Electron delocalization occurs in the complex system where a N, N'-dimethyloxamidate binds two [Mo2] units within two fused six-membered rings. In this case, the mixed-valence complex has a symmetric molecular structure, implying that the odd electron is fully delocalized over two [Mo2]units. Strong metal-metal interaction is also evidenced by intervalence charge transfer of the mixed-valence species and the diamanetism of the doubly oxidized complex. Remarkably, two isomers varying in linkage conformation, namely, alpha and beta, have been isolated as diaryloxamidate ligands are used as the linker. Studies on the neutral and the oxidized compounds of the two isomers by employing various techniques consistently show that in the alpha form intramolecular electron transfer is blocked , while in the beta form, the electrons are delocalized over the two [Mo2] units. Thus, the mixed-valence complexes of the two isomers are appropriately described by alpha-[Mo2]0(oxamidate)[Mo2]1+ and beta- [Mo2]0.5+(oxamidate)[Mo2]0.5+ respectively.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references (leaves 162-168). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references (leaves 162-168). Also available on the Internet.