{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70247"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70247","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Some Organometallic Chemistry of Tungsten-Triosmium Cluster Compounds","abstract":"The present study involves the synthesis, structure, and reactivity of new tungsten-triosmium (WOs(,3)) cluster compounds. The presence of a tungsten atom in the cluster framework imparts a considerably different reactivity pattern than that observed in triosmium chemistry.","abstract_html":"The present study involves the synthesis, structure, and reactivity of new tungsten-triosmium (WOs(,3)) cluster compounds. The presence of a tungsten atom in the cluster framework imparts a considerably different reactivity pattern than that observed in triosmium chemistry.","abstract_has_math":false,"creators":["Park, Joon-Taik"],"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":"2014-12-15T23:18:08Z","date_published":"2014-12-15T23:18:08Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8410016"],"render_values":[{"text":"(UMI)AAI8410016","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70247","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Park, Joon-Taik"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:08Z","10000-01-01","1983"]},{"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/2142/70247","(UMI)AAI8410016"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The present study involves the synthesis, structure, and reactivity of new tungsten-triosmium (WOs(,3)) cluster compounds. The presence of a tungsten atom in the cluster framework imparts a considerably different reactivity pattern than that observed in triosmium chemistry.","The reaction of H(,2)Os(,3)(CO)(,10) with CpW(CO)(,2)(CTol){Cp = (eta)('5)-C(,5)H(,5); Tol = p - C(,6)H(,4)CH(,3)} yields three products under mild conditions: CpWOs(,3)(CO)(,11){(mu)(,3)-(eta)('2)-C(O)CH(,2)Tol} (1), Cp(,2)W(,2)Os(CO)(,7)((mu)(,3)-(eta)('2)-C(,2)Tol(,2)) (2), and CpWOs(,3)(CO)(,10)((mu)(,3)-CTol)(,2)H (3). Compound 1 undergoes acyl CO bond scission to provide the doubly-bridging oxo-alkylidyne compound, CpWOs(,3)(CO)(,9)((mu)-O)((mu)(,3)-CCH(,2)Tol) (4). Compound 3 undergoes a degenerate framework rearrangement that interchanges the two inequivalent (mu)(,3)-CTol groups. In addition, the dialkylidyne compound 3 clearly transforms to a symmetrical dialkylidyne complex, CpWOs(,3)(CO)(,9)((mu)(,3)-CTol)(,2)H (5). Compound 4 exhibits reactivity such as oxidative addition of a benzylic hydrogen and conversion to a hydrido-alkylidene compound by dihydrogen, yielding CpWOs(,3)(CO)(,9)((mu)-O)((mu)-CCHTol)H (6) and two isomers of CpWOs(,3)(CO)(,9)((mu)-O)((mu)-CHCH(,2)Tol)H (7), respectively.","Reactions of Os(,3)(CO)(,10)(NCMe)(,2) and Os(,3)(CO)(,9)(C(,2)Ph)(,2) with CpW(CO)(,2)(CTol) provides the complexes of CpWOs(,3)(CO)(,11)((mu)(,3)-CTol) (8) and CpWOs(,3)(CO)(,10)-(C(,3)Ph(,2)Tol) (9), respectively.(,)","Reactions of CpWOs(,3)(CO)(,12)H with a series of alkynes (RC(TBOND)CR) have resulted in the isolation of two isomeric alkyne derivatives, CpWOs(,3)(CO)(,10)((mu)(,3)-(eta)('2)-C(,2)R(,2))H. Some of these complexes (R = CO(,2)Et, Cf(,3)) undergo irreversible thermal isomerization from one isomer to the other. Diaryl alkyne complexes (R = Ph, Tol) undergo facile intramolecular C(TBOND)C bond scission reactions to yield the corresponding dialkyidyne derivatives, CpWOs(,3)(CO)(,9)((mu)(,3)-CR)(,2)H.","Made available in DSpace on 2014-12-15T23:18:08Z (GMT). No. of bitstreams: 1 8410016.pdf: 4566490 bytes, checksum: d152422cea2906d0475cc9124c5bc339 (MD5) Previous issue date: 1983","Embargo set by: Seth Robbins for item 70413 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","173 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1983."]},{"key":"dc:title","label":"Title","values":["Some Organometallic Chemistry of Tungsten-Triosmium Cluster Compounds"]}]}],"canonical_facts":{"dc:creator":["Park, Joon-Taik"],"dc:date":["2014-12-15T23:18:08Z","10000-01-01","1983"],"dc:description":["The present study involves the synthesis, structure, and reactivity of new tungsten-triosmium (WOs(,3)) cluster compounds. The presence of a tungsten atom in the cluster framework imparts a considerably different reactivity pattern than that observed in triosmium chemistry.","The reaction of H(,2)Os(,3)(CO)(,10) with CpW(CO)(,2)(CTol){Cp = (eta)('5)-C(,5)H(,5); Tol = p - C(,6)H(,4)CH(,3)} yields three products under mild conditions: CpWOs(,3)(CO)(,11){(mu)(,3)-(eta)('2)-C(O)CH(,2)Tol} (1), Cp(,2)W(,2)Os(CO)(,7)((mu)(,3)-(eta)('2)-C(,2)Tol(,2)) (2), and CpWOs(,3)(CO)(,10)((mu)(,3)-CTol)(,2)H (3). Compound 1 undergoes acyl CO bond scission to provide the doubly-bridging oxo-alkylidyne compound, CpWOs(,3)(CO)(,9)((mu)-O)((mu)(,3)-CCH(,2)Tol) (4). Compound 3 undergoes a degenerate framework rearrangement that interchanges the two inequivalent (mu)(,3)-CTol groups. In addition, the dialkylidyne compound 3 clearly transforms to a symmetrical dialkylidyne complex, CpWOs(,3)(CO)(,9)((mu)(,3)-CTol)(,2)H (5). Compound 4 exhibits reactivity such as oxidative addition of a benzylic hydrogen and conversion to a hydrido-alkylidene compound by dihydrogen, yielding CpWOs(,3)(CO)(,9)((mu)-O)((mu)-CCHTol)H (6) and two isomers of CpWOs(,3)(CO)(,9)((mu)-O)((mu)-CHCH(,2)Tol)H (7), respectively.","Reactions of Os(,3)(CO)(,10)(NCMe)(,2) and Os(,3)(CO)(,9)(C(,2)Ph)(,2) with CpW(CO)(,2)(CTol) provides the complexes of CpWOs(,3)(CO)(,11)((mu)(,3)-CTol) (8) and CpWOs(,3)(CO)(,10)-(C(,3)Ph(,2)Tol) (9), respectively.(,)","Reactions of CpWOs(,3)(CO)(,12)H with a series of alkynes (RC(TBOND)CR) have resulted in the isolation of two isomeric alkyne derivatives, CpWOs(,3)(CO)(,10)((mu)(,3)-(eta)('2)-C(,2)R(,2))H. Some of these complexes (R = CO(,2)Et, Cf(,3)) undergo irreversible thermal isomerization from one isomer to the other. Diaryl alkyne complexes (R = Ph, Tol) undergo facile intramolecular C(TBOND)C bond scission reactions to yield the corresponding dialkyidyne derivatives, CpWOs(,3)(CO)(,9)((mu)(,3)-CR)(,2)H.","Made available in DSpace on 2014-12-15T23:18:08Z (GMT). No. of bitstreams: 1 8410016.pdf: 4566490 bytes, checksum: d152422cea2906d0475cc9124c5bc339 (MD5) Previous issue date: 1983","Embargo set by: Seth Robbins for item 70413 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","173 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1983."],"dc:identifier":["http://hdl.handle.net/2142/70247","(UMI)AAI8410016"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Some Organometallic Chemistry of Tungsten-Triosmium Cluster 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"}