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Synthesis and Reactivity of Dichalcogenide and Substituted Dichalcogenide Ligands in Molecular and Nonmolecular Compounds Hoots, John Edward 2014-12-15T23:18:03Z 2014-12-15T23:18:03Z 10000-01-01 1984 1984 An array of mono- and 1,2-disubstituted derivatives of the (eta)('2)-S(,2) and Se(,2) ligand systems have been prepared. The reactivity and distinctive ('1)H NMR spectroscopic behavior of complexes containing these ligands have been examined. The reactivity studies were extended to solid-state metal sulfides, particularly pyrite (FeS(,2)). {Ir(S(,2)CH(,3))(dppe)(,2)}('2+) (dppe = Ph(,2)PCH(,2)CH(,2)PPh(,2)) is a potent chalcogen-transfer reagent towards nucleophiles (Ph(,3)P, CH(,3)NC, CN('-)) and several reaction pathways have been observed. The multistep reaction with 2 CH(,3)NC produced cis-{Ir(CH(,3)NC)(SCH(,3))(dppe)(,2)}('2+) and serves as a model for the Oxirane olefin epoxidation process. Organoperacids effect facile oxidation of {Ir(E(,2))(dppe)(,2)}('+) (E = S, Se) complexes to the (eta)('2)-S(,2)O, S(,2)O(,2), and Se(,2)O derivatives. Likewise, oxidation of (C(,5)H(,5))Nb(S(,2))Cl produced an (eta)('2)-S(,2)O ligand. The reaction of {Ir(S(,2)O(,x))(dppe)(,2)}('+) (x = 1,2) with CH(,3)OSO(,2)F formed the corresponding O-alkylated (eta)('2)-S(,2)O(,x)CH(,3) derivatives. Attempted synthesis of the first (eta)('1) or (eta)('2)-SO ligand by sulfur-abstraction from complexes containing (eta)('2)-S(,2)O ligands was unsuccessful, but formation of {Ir(SeS)(dppe)(,2)}('+) was observed in the reaction of Ir(dppe)(,2)('+) and (CH(,3)C(,5)H(,4))(,2)Ti S(,x)Se(,5-x). A stabilized form of the SO unit, the O-methyl thioperoxide ligand, was observed in Ir((eta)('1)-SOCH(,3))(CH(,3)NC)(dppe)(,2)('2+) and produced by abstraction of the unsubstituted sulfur in {Ir(S(,2)OCH(,3))(dppe)(,2)}('2+) with CH(,3)NC. Formation of pollutants, such as SO(,2), from the decomposition of pyrite has remained a major barrier to the increased use of coal as a fuel source. Desulfurization of pyrite with (n-C(,4)H(,9))(,3)P at 260(DEGREES)C produced an equilibrium mixture of FeS and Fe(,0.95)S and the corresponding phosphine sulfide: Partial desulfurization of an array of metal sulfides (MoS(,3), CoS(,2), Cu(,2)S) with organophosphines demonstrated this reaction's generality. Catalytic desulfurization of pyrite with R(,3)P reagents was accomplished by addition of iron as a sulfur-receptor. An overall rate of (TURN)40 turnovers/hr and 85% conversion to Fe(,0.99)S was observed with an 100:1 ratio of FeS(,2) to (n-C(,4)H(,9))(,3)P at 300(DEGREES)C. The stoichiometric organophosphine desulfurization reaction was applied to a dried sample of Illinois coal (2.0% FeS(,2)). Complete conversion of pyrite to pyrrhotite and 90% recovery of free organophosphine sulfide was accomplished. Made available in DSpace on 2014-12-15T23:18:03Z (GMT). No. of bitstreams: 1 8409781.pdf: 5805622 bytes, checksum: 60dac39d6a2f2a4c0c68db199b2275e8 (MD5) Previous issue date: 1984 Embargo set by: Seth Robbins for item 70401 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 193 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984. http://hdl.handle.net/2142/70235 (UMI)AAI8409781 Chemistry, Inorganic text Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.