{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70235"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70235","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis and Reactivity of Dichalcogenide and Substituted Dichalcogenide Ligands in Molecular and Nonmolecular Compounds","abstract":"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)).","abstract_html":"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)).","abstract_has_math":false,"creators":["Hoots, John Edward"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:18:03Z","date_published":"2014-12-15T23:18:03Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8409781"],"render_values":[{"text":"(UMI)AAI8409781","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70235","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Hoots, John Edward"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:03Z","10000-01-01","1984"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Inorganic"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/70235","(UMI)AAI8409781"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["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."]},{"key":"dc:title","label":"Title","values":["Synthesis and Reactivity of Dichalcogenide and Substituted Dichalcogenide Ligands in Molecular and Nonmolecular Compounds"]}]}],"canonical_facts":{"dc:creator":["Hoots, John Edward"],"dc:date":["2014-12-15T23:18:03Z","10000-01-01","1984"],"dc:description":["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."],"dc:identifier":["http://hdl.handle.net/2142/70235","(UMI)AAI8409781"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis and Reactivity of Dichalcogenide and Substituted Dichalcogenide Ligands in Molecular and Nonmolecular Compounds"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:26:02Z"}