Metal dithiolenes [M(S2C2R2)n] have been studied for decades because of their interesting chemical and spectroscopic properties, which are related to the unusual electronic properties of the dithiolene ligand. The ligand-based reactivity of metal bisdithiolenes [M(S2C2R2)2] toward alkenes has been proposed for use in alkene purification schemes. According to the proposal, compounds Ni(S2C2R2)2 (R=CF3,CN) react with simple alkenes to form stable S,S-interligand adducts and the alkene can be released from the adduct by reduction. We showed that Ni(S2C2(CF3)2)2 reacts with ethylene and 1-hexene to form, preferentially, S,S-intraligand adducts, which rapidly decompose to inactive metal-containing materials and dihydrodithiins. However, the product selectivity can be significantly modified so that stable S,S-interligand adducts are obtained as dominant products by adding [Ni(S2C2(CF3)2)2]- to Ni(S2C2(CF3)2)2/alkene reaction mixtures. Mechanistic implications are discussed. Next, the reactions of Pt(S2C2(CF3)2)2 with 2,3-dimethyl-1,3-butadiene are addressed. Prior to our report, only symmetry-allowed S,S-interligand adducts had been observed as products in the reactions between conjugated dienes and metal bisdithiolenes. We discovered a novel mode of diene binding, where two dienes bind to one dithiolene ligand of Pt(S2C2(CF3)2)2, in an C,S-intraligand fashion, forming a new chiral bisthioether ligand. From bisdithiolenes, the focus shifts to new mixed-ligand molybdenum trisdithiolenes [Mo(S2C2(CF3)2)2(S2C6H4) and Mo(S2C6H4)2(S2C2(CF3)2)]. These complexes rapidly and cleanly bind ethylene, in an S,S-intraligand fashion, as predicted by MO arguments. The resulting intraligand adducts are sufficiently stable to be characterized, in contrast to the nickel bisdithiolene case. The metal-chelated dihydrobenzodithiin, formed upon ethylene addition, can be substituted with a variety of donor ligands, allowing access to new types of molybdenum dithiolenes. We have recently extended these studies to catalytic reactions: Mo(S2C2(CF3)2)2(S2C6H4) was used as a catalyst to form dihydrobenzodithiins from (S2C6H4)2 and a variety of alkenes, in the first example of dithiolene-based reactivity being exploited for carbon-heteroatom bond-forming catalysis. Finally, the synthesis, characterization and redox reactivity of a new Fe2Ni bis-double-decker complex is described, demonstrating for the first time a sandwich complex of a metal bisdithiolene with both NiS2C2 rings in an η5 π-donating mode. For the radical cation, experimental and computation evidence indicates that the lone electron is delocalized over the entire molecule.

This study highlights the importance of the anion in the electrochemical uptake of lithium by metal phosphides. It is shown through a variety of <em>in-situ</em> and <em>ex-situ</em> analytical techniques that the redox active centers in three different systems (MnP<i>₄</i>, FeP<i>₂</i>, and CoP<i>₃</i>) are not necessarily cationic but can rest almost entirely upon the anionic network, thanks to the high degree of covalency of the metal-phosphorus bond and strong P-character of the uppermost filled electronic bands in the phosphides. The electrochemical mechanism responsible for reversible Li uptake depends on the transition metal, whether a lithiated ternary phase exists in the phase diagram with the same M:P stoichiometry as the binary phase, and on the structure of the starting phase. When both binary and lithiated ternary phases of the transition metal exist, as in the case of MnP<i>₄</i> and Li<i>₇</i>MnP<i>₄</i>, a semi-topotactic phase transformation between binary and ternary phases occurs upon lithium uptake and removal. When only the binary phase exists two different behaviours are observed. In the FeP<i>₂</i> system, lithium uptake leads to the formation of an amorphous material in which short-range order persists; removal of lithium reforms some the long-range order bonds. In the case of CoP<i>₃</i>, lithium uptake results in phase decomposition to metallic cobalt plus lithium triphosphide, which becomes the active material for the subsequent cycles.

This study highlights the importance of the anion in the electrochemical uptake of lithium by metal phosphides. It is shown through a variety of <em>in-situ</em> and <em>ex-situ</em> analytical techniques that the redox active centers in three different systems (MnP<i>₄</i>, FeP<i>₂</i>, and CoP<i>₃</i>) are not necessarily cationic but can rest almost entirely upon the anionic network, thanks to the high degree of covalency of the metal-phosphorus bond and strong P-character of the uppermost filled electronic bands in the phosphides. The electrochemical mechanism responsible for reversible Li uptake depends on the transition metal, whether a lithiated ternary phase exists in the phase diagram with the same M:P stoichiometry as the binary phase, and on the structure of the starting phase. When both binary and lithiated ternary phases of the transition metal exist, as in the case of MnP<i>₄</i> and Li<i>₇</i>MnP<i>₄</i>, a semi-topotactic phase transformation between binary and ternary phases occurs upon lithium uptake and removal. When only the binary phase exists two different behaviours are observed. In the FeP<i>₂</i> system, lithium uptake leads to the formation of an amorphous material in which short-range order persists; removal of lithium reforms some the long-range order bonds. In the case of CoP<i>₃</i>, lithium uptake results in phase decomposition to metallic cobalt plus lithium triphosphide, which becomes the active material for the subsequent cycles.

ABSTRACT Key words: PCDD/FS , aromatic precursor compounds , transition metal catalysts , chlorine donor , surface of fly ash particles In the last 20 years , increasing concern has focused on the environmental chemicals that mimic hormone functions , some of them toxic , which producing cancer , suppression of the immune system , and death from undefined causes . These chemicals are not made intentionally , but are formed as contaminants in combustion sources , including PCDD/FS of dioxin-like compounds that emitted from municipal solid waste incinerators (MWSI) and hazardous waste incinerators (HWI) . This study investigated the role that fly-ash plays in the formation of PCDD/FS using a commercial scale fluidized bed waste incinerators (FBWI) , which rated capacity at 3750000 kcal/hr (LHV) . In this design , a lay of sand is placed on the bottom of the combustion chamber. During combustion, the hot gases are channeled through the sand and crushed solid waste at relatively high velocity . This generated about eight times more mass of fly-ash will be produced from combustion zone than the others, and also makes much greater of PCDD/FS through the air pollutants control devices(APCD) to emission stack . The general reaction in this formation pathway is an interaction between an aromatic precursor compound and chlorine promoted by a transition metal catalyst on a reactive fly-ash surface. Since these reactions involve heterogenous chemistry , the rate of emissions is less depended on reactant concentration than conditions that promote formation such as temperature , retention time , transition metal catalysts (e , g,. Cu , Fe , Pb , Zn , Sn) and availability on catalytic surfaces of fly ash particle . These forming conditions will be proceeding a series of well study and experiment on fly-ashes from 4 zones (F1 , F2 ,F3 , F4) of FBWI . PCDD/FS synthesis from combustion of FBWI can potentially be explained by three principal mechanisms that results can be divided into several major parts as follows¡G 1. The fly-ash from zone F3 generated about 47 times more mass of PCDD/FS than zone F1 . 2. The F3 fly-ash proved to be the most active catalytic (Cu , Zn) medium , despite similarities with respect to specific surface area and average pore diameters . In addition , there are up to 75.9 percent by weight of Zn and 97.6 percent of Cu has been found in F3 of overall ashes. 3. In both fly- ash and transition metal catalysts in formation mechanisms are the dominant controlling factor for rates of PCDD/FS.

Thesis (M. Sc.)--University of Canterbury, 2009. / Typescript (photocopy). "June 2009." Includes bibliographical references. Also available via the World Wide Web.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 148-156).

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 136-144).

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 150-159). Also available on the Internet.

Thesis (M.S.)--Rutgers University, 2009. / "Graduate Program in Mechanical and Aerospace Engineering." Includes bibliographical references (p. 82-83).

Thesis (Ph. D.)--University of Missouri-Columbia, 2003. / Typescript. Vita. Includes bibliographical references (leaves 110-113). Also available on the Internet.