{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84492"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84492","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 Polysulfido Metal Complexes","abstract":"The final area of thesis research is the investigation iridium polysulfido complexes. Desulfurization of (NBun4 )Ir(S6)3 with excess PPh3 yields a 30 e-- dimer Ir2S2(PPh4) 4. Crystallographic analysis of Ir2S2(PPh 4)4 reveals a bitetrahedral structure with a pair of mu-S atoms. Two equiv of H2 add to Ir2S2(PPh 4)4 to yield Ir2S(SH)H3(PPh3) 4. The first addition of H2 to Ir2S2(PPh 4)4 proceeds homolytically while the second addition proceeds formally heterolytically. One equiv of H2 adds to Ir2S 2(PPh4)4 to yield Ir2S2H 2(PPh3)4. Low temperature H2 addition to Ir2S2(PPh4)4 reveals an intermediate. This intermediate is a kinetic isomer of compound Ir2S(SH)H 3(PPh3)4. The conversion of this intermediate to Ir2S(SH)H3(PPh3)4 is a first-order reaction with an approximate rate constant of 5 x 10-5 s-1 at -20°C. With a 50 fold excess of H2, the production of Ir2S(SH)H3(PPh 3)4 by the addition of H2 to Ir2S 2H2(PPh3)4 is also a first-order reaction with an approximate rate constant of 3 x 10-5 s -1.","abstract_html":"The final area of thesis research is the investigation iridium polysulfido complexes. Desulfurization of (NBun4 )Ir(S6)3 with excess PPh3 yields a 30 e-- dimer Ir2S2(PPh4) 4. Crystallographic analysis of Ir2S2(PPh 4)4 reveals a bitetrahedral structure with a pair of mu-S atoms. Two equiv of H2 add to Ir2S2(PPh 4)4 to yield Ir2S(SH)H3(PPh3) 4. The first addition of H2 to Ir2S2(PPh 4)4 proceeds homolytically while the second addition proceeds formally heterolytically. One equiv of H2 adds to Ir2S 2(PPh4)4 to yield Ir2S2H 2(PPh3)4. Low temperature H2 addition to Ir2S2(PPh4)4 reveals an intermediate. This intermediate is a kinetic isomer of compound Ir2S(SH)H 3(PPh3)4. The conversion of this intermediate to Ir2S(SH)H3(PPh3)4 is a first-order reaction with an approximate rate constant of 5 x 10-5 s-1 at -20°C. With a 50 fold excess of H2, the production of Ir2S(SH)H3(PPh 3)4 by the addition of H2 to Ir2S 2H2(PPh3)4 is also a first-order reaction with an approximate rate constant of 3 x 10-5 s -1.","abstract_has_math":false,"creators":["Pafford, Robert Joseph, IV"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:14:47Z","date_published":"2015-09-25T22:14:47Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI9990103"],"render_values":[{"text":"(MiAaPQ)AAI9990103","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84492","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Rauchfuss, Thomas B."]},{"key":"dc:creator","label":"Author","values":["Pafford, Robert Joseph, IV"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:47Z","10000-01-01","2000"]},{"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":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/84492","(MiAaPQ)AAI9990103"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The final area of thesis research is the investigation iridium polysulfido complexes. Desulfurization of (NBun4 )Ir(S6)3 with excess PPh3 yields a 30 e-- dimer Ir2S2(PPh4) 4. Crystallographic analysis of Ir2S2(PPh 4)4 reveals a bitetrahedral structure with a pair of mu-S atoms. Two equiv of H2 add to Ir2S2(PPh 4)4 to yield Ir2S(SH)H3(PPh3) 4. The first addition of H2 to Ir2S2(PPh 4)4 proceeds homolytically while the second addition proceeds formally heterolytically. One equiv of H2 adds to Ir2S 2(PPh4)4 to yield Ir2S2H 2(PPh3)4. Low temperature H2 addition to Ir2S2(PPh4)4 reveals an intermediate. This intermediate is a kinetic isomer of compound Ir2S(SH)H 3(PPh3)4. The conversion of this intermediate to Ir2S(SH)H3(PPh3)4 is a first-order reaction with an approximate rate constant of 5 x 10-5 s-1 at -20°C. With a 50 fold excess of H2, the production of Ir2S(SH)H3(PPh 3)4 by the addition of H2 to Ir2S 2H2(PPh3)4 is also a first-order reaction with an approximate rate constant of 3 x 10-5 s -1.","Made available in DSpace on 2015-09-25T22:14:47Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9990103.pdf: 5365845 bytes, checksum: f802e12f56323872839f2eddacc8dfc0 (MD5) Previous issue date: 2000","Embargo set by: Seth Robbins for item 85773 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","141 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2000."]},{"key":"dc:title","label":"Title","values":["Synthesis and Reactivity of Polysulfido Metal Complexes"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Pafford, Robert Joseph, IV"],"dc:date":["2015-09-25T22:14:47Z","10000-01-01","2000"],"dc:description":["The final area of thesis research is the investigation iridium polysulfido complexes. Desulfurization of (NBun4 )Ir(S6)3 with excess PPh3 yields a 30 e-- dimer Ir2S2(PPh4) 4. Crystallographic analysis of Ir2S2(PPh 4)4 reveals a bitetrahedral structure with a pair of mu-S atoms. Two equiv of H2 add to Ir2S2(PPh 4)4 to yield Ir2S(SH)H3(PPh3) 4. The first addition of H2 to Ir2S2(PPh 4)4 proceeds homolytically while the second addition proceeds formally heterolytically. One equiv of H2 adds to Ir2S 2(PPh4)4 to yield Ir2S2H 2(PPh3)4. Low temperature H2 addition to Ir2S2(PPh4)4 reveals an intermediate. This intermediate is a kinetic isomer of compound Ir2S(SH)H 3(PPh3)4. The conversion of this intermediate to Ir2S(SH)H3(PPh3)4 is a first-order reaction with an approximate rate constant of 5 x 10-5 s-1 at -20°C. With a 50 fold excess of H2, the production of Ir2S(SH)H3(PPh 3)4 by the addition of H2 to Ir2S 2H2(PPh3)4 is also a first-order reaction with an approximate rate constant of 3 x 10-5 s -1.","Made available in DSpace on 2015-09-25T22:14:47Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9990103.pdf: 5365845 bytes, checksum: f802e12f56323872839f2eddacc8dfc0 (MD5) Previous issue date: 2000","Embargo set by: Seth Robbins for item 85773 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","141 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2000."],"dc:identifier":["http://hdl.handle.net/2142/84492","(MiAaPQ)AAI9990103"],"dc:language":["eng"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Synthesis and Reactivity of Polysulfido Metal Complexes"],"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":"2026-07-22T22:26:23Z"}