{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70343"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70343","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Model Chemistry on Metal Surfaces: Synthesis, Structure and Reactivity Studies of Tungsten-Osmium Mixed-Metal Clusters","abstract":"Reaction of H(,2)Os(,3)(CO)(,10) with CpW(CO)(,2)(CTol) provides four mixed-metal compounds, i.e. CpWOs(,3)(CO)(,11) (mu)(,3)-(eta)('2)-C(O)CH(,2)Tol (1), CpWOs(,3)(CO)(,10)((mu)(,3)-CTol)(,2)H (2), Cp(,2)W(,2)Os(CO)-(,7)((mu)(,3)-(eta)('2)-C(,2)Tol(,2)) (3),","abstract_html":"Reaction of H(,2)Os(,3)(CO)(,10) with CpW(CO)(,2)(CTol) provides four mixed-metal compounds, i.e. CpWOs(,3)(CO)(,11) (mu)(,3)-(eta)('2)-C(O)CH(,2)Tol (1), CpWOs(,3)(CO)(,10)((mu)(,3)-CTol)(,2)H (2), Cp(,2)W(,2)Os(CO)-(,7)((mu)(,3)-(eta)('2)-C(,2)Tol(,2)) (3),","abstract_has_math":false,"creators":["Chi, Yun"],"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":"2014-12-15T23:18:49Z","date_published":"2014-12-15T23:18:49Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8701460"],"render_values":[{"text":"(UMI)AAI8701460","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70343","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Chi, Yun"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:49Z","10000-01-01","1986"]},{"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/2142/70343","(UMI)AAI8701460"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Reaction of H(,2)Os(,3)(CO)(,10) with CpW(CO)(,2)(CTol) provides four mixed-metal compounds, i.e. CpWOs(,3)(CO)(,11) (mu)(,3)-(eta)('2)-C(O)CH(,2)Tol (1), CpWOs(,3)(CO)(,10)((mu)(,3)-CTol)(,2)H (2), Cp(,2)W(,2)Os(CO)-(,7)((mu)(,3)-(eta)('2)-C(,2)Tol(,2)) (3),","and CpW(CO)(,3) ((mu)-H)(,2)Os(,3)(CO)(,9)((mu)(,3)-CTol) (4). Reaction of 4 with Cp- W(CO)(,2)-(CTol) give complex 2. Pyrolysis of 1 and 3 gives CpWOs(,3)- (CO)(,9)((mu)-O)((mu)(,3)-CCH(,2)Tol) (5) and Cp(,2)W(,2)Os(CO)(,5)((mu)-CTol)((mu)(,3)-CTol), respectively. Compound 5 undergoes monocarbonylation to give","CpW(CO)(,2)(CTol) provides a TBP pentanuclear cluster CpW(,2)Os(,3)- (CO)(,9)((mu)(,3)-O)((mu)(,3)-(eta)('2)-CCHTol); VT-('1)H NMR studies show that the vinylidene ligand undergoes a one-third cycle of circumambulation. (Abstract shortened with permission of author.)","CpWOs(,3)(CO)(,10)((mu)-O)((mu)(,3)-CCH(,2)Tol), which is an intermediate for the acyl C-O bond scission process (1 (--->) 5). Pyrolysis of 5 gives CpWOs(,3)(CO)(,9)((mu)-H)((mu)-O)((mu)-CCHTol).","Treatment of 5 with Ph-C(TBOND)C-Ph provides a butterfly cluster Cp- WOs(,3)(CO)(,8)((mu)-O)((mu)(,3)-CCH(,2)-Tol)((mu)(,3)-(eta)('2)-C(,2)Ph(,2)). This complex under- goes reaction under an H(,2) atmosphere, or decarbonylation to give","CpWOs(,3)(CO)(,7)((mu)-H)(,2)((mu)-O)((mu)(,4)-(eta)('2)-CCHTol)(CH=CHPh) or CpWOs(,3)- (CO)(,7)((mu)-O)((mu)-(eta)('2)-CHCHTol)(C(,2)Ph(,2)), respectively.","Reaction of 5 with various HX reagents, X = H, Cl, Br and S-C(,6)H(,5), provides three alkylidene complexes with the formulation of CpW- Os(,3)(CO)(,9)((mu)-X)((mu)-O)((mu)-CHCH(,2)Tol) (isomers-a, b and c). The inter- conversion of a and b, and of b and c involves H-migration and alkyl- idene isomerization, respectively. For the alkylidene complexes, X (NOT=) H, only b and c isomers are isolated, in which c is the thermodynam- ically more stable form. Treatment of CpWOs(,3)(CO)(,9)((mu)-Cl)((mu)-O)((mu)-CHCH(,2)Tol) (isomers b and c) with gaseous BCl(,3) generates CpWOs(,3)- (CO)(,9)((mu)-Cl)((mu)-OBCl(,3))((mu)-CHCH(,2)Tol) in which BCl(,3) has been found to coordinate the bridging oxo-ligand, thereby activating the reverse alkylidene isomerization from isomers c to b.","Reaction of 5 with cyclooctene under N(,2) or H(,2) affords CpWOs(,3)- (CO)(,8)(C(,8)H(,14))((mu)-H)((mu)-O)((mu)-CCHTol) (6), or CpWOs(,3)(CO)(,8)(C(,8)H(,14))((mu)-H)((mu)-O)((mu)-CHCH(,2)Tol), respectively. The reaction presumably pro- ceeds by cyclooctene substitution to give an alkylidyne intermediate","CpWOs(,3)(CO)(,8)(C(,8)H(,14))((mu)-O)((mu)(,3)-CCH(,2)Tol). Compound 6 undergoes olefin exchange with ethylene to provide CpWOs(,3)(CO)(,8)(C(,2)H(,4))((mu)-H)- ((mu)-O)((mu)-CCHTol), in that the C(,2)H(,4) group is coordinated to an Os atom associated with the bridging hydride; the reversible C(,2)H(,4) inser- tion into Os-H-Os bond is established by dynamic NMR techniques.","Exchange with either dimethyl meleate (fumarate) gives another extreme of such olefin insertion reaction, an alkyl complex CpWOs(,3)- (CO)(,8)((mu)-O)((mu)-CCHTol) CH(CO(,2)CH(,3))CH(,2)(CO(,2)CH(,3)) being isolated.","The reversible insertion of an alkyne into the Os-H-Os bond is explored by exchange of C(,8)H(,14) with Ph-C(TBOND)C-Ph, giving CpWOs(,3)- (CO)(,8)((mu)(,3)-O)((mu)(,3)-(eta)('2)-CCHTol)((mu)-(eta)-CPh=CHPh). Reaction of 6 with","Made available in DSpace on 2014-12-15T23:18:49Z (GMT). No. of bitstreams: 1 8701460.pdf: 9009604 bytes, checksum: 13a29d4c95361f438afee271e03b4f34 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70509 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","239 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."]},{"key":"dc:title","label":"Title","values":["Model Chemistry on Metal Surfaces: Synthesis, Structure and Reactivity Studies of Tungsten-Osmium Mixed-Metal Clusters"]}]}],"canonical_facts":{"dc:creator":["Chi, Yun"],"dc:date":["2014-12-15T23:18:49Z","10000-01-01","1986"],"dc:description":["Reaction of H(,2)Os(,3)(CO)(,10) with CpW(CO)(,2)(CTol) provides four mixed-metal compounds, i.e. CpWOs(,3)(CO)(,11) (mu)(,3)-(eta)('2)-C(O)CH(,2)Tol (1), CpWOs(,3)(CO)(,10)((mu)(,3)-CTol)(,2)H (2), Cp(,2)W(,2)Os(CO)-(,7)((mu)(,3)-(eta)('2)-C(,2)Tol(,2)) (3),","and CpW(CO)(,3) ((mu)-H)(,2)Os(,3)(CO)(,9)((mu)(,3)-CTol) (4). Reaction of 4 with Cp- W(CO)(,2)-(CTol) give complex 2. Pyrolysis of 1 and 3 gives CpWOs(,3)- (CO)(,9)((mu)-O)((mu)(,3)-CCH(,2)Tol) (5) and Cp(,2)W(,2)Os(CO)(,5)((mu)-CTol)((mu)(,3)-CTol), respectively. Compound 5 undergoes monocarbonylation to give","CpW(CO)(,2)(CTol) provides a TBP pentanuclear cluster CpW(,2)Os(,3)- (CO)(,9)((mu)(,3)-O)((mu)(,3)-(eta)('2)-CCHTol); VT-('1)H NMR studies show that the vinylidene ligand undergoes a one-third cycle of circumambulation. (Abstract shortened with permission of author.)","CpWOs(,3)(CO)(,10)((mu)-O)((mu)(,3)-CCH(,2)Tol), which is an intermediate for the acyl C-O bond scission process (1 (--->) 5). Pyrolysis of 5 gives CpWOs(,3)(CO)(,9)((mu)-H)((mu)-O)((mu)-CCHTol).","Treatment of 5 with Ph-C(TBOND)C-Ph provides a butterfly cluster Cp- WOs(,3)(CO)(,8)((mu)-O)((mu)(,3)-CCH(,2)-Tol)((mu)(,3)-(eta)('2)-C(,2)Ph(,2)). This complex under- goes reaction under an H(,2) atmosphere, or decarbonylation to give","CpWOs(,3)(CO)(,7)((mu)-H)(,2)((mu)-O)((mu)(,4)-(eta)('2)-CCHTol)(CH=CHPh) or CpWOs(,3)- (CO)(,7)((mu)-O)((mu)-(eta)('2)-CHCHTol)(C(,2)Ph(,2)), respectively.","Reaction of 5 with various HX reagents, X = H, Cl, Br and S-C(,6)H(,5), provides three alkylidene complexes with the formulation of CpW- Os(,3)(CO)(,9)((mu)-X)((mu)-O)((mu)-CHCH(,2)Tol) (isomers-a, b and c). The inter- conversion of a and b, and of b and c involves H-migration and alkyl- idene isomerization, respectively. For the alkylidene complexes, X (NOT=) H, only b and c isomers are isolated, in which c is the thermodynam- ically more stable form. Treatment of CpWOs(,3)(CO)(,9)((mu)-Cl)((mu)-O)((mu)-CHCH(,2)Tol) (isomers b and c) with gaseous BCl(,3) generates CpWOs(,3)- (CO)(,9)((mu)-Cl)((mu)-OBCl(,3))((mu)-CHCH(,2)Tol) in which BCl(,3) has been found to coordinate the bridging oxo-ligand, thereby activating the reverse alkylidene isomerization from isomers c to b.","Reaction of 5 with cyclooctene under N(,2) or H(,2) affords CpWOs(,3)- (CO)(,8)(C(,8)H(,14))((mu)-H)((mu)-O)((mu)-CCHTol) (6), or CpWOs(,3)(CO)(,8)(C(,8)H(,14))((mu)-H)((mu)-O)((mu)-CHCH(,2)Tol), respectively. The reaction presumably pro- ceeds by cyclooctene substitution to give an alkylidyne intermediate","CpWOs(,3)(CO)(,8)(C(,8)H(,14))((mu)-O)((mu)(,3)-CCH(,2)Tol). Compound 6 undergoes olefin exchange with ethylene to provide CpWOs(,3)(CO)(,8)(C(,2)H(,4))((mu)-H)- ((mu)-O)((mu)-CCHTol), in that the C(,2)H(,4) group is coordinated to an Os atom associated with the bridging hydride; the reversible C(,2)H(,4) inser- tion into Os-H-Os bond is established by dynamic NMR techniques.","Exchange with either dimethyl meleate (fumarate) gives another extreme of such olefin insertion reaction, an alkyl complex CpWOs(,3)- (CO)(,8)((mu)-O)((mu)-CCHTol) CH(CO(,2)CH(,3))CH(,2)(CO(,2)CH(,3)) being isolated.","The reversible insertion of an alkyne into the Os-H-Os bond is explored by exchange of C(,8)H(,14) with Ph-C(TBOND)C-Ph, giving CpWOs(,3)- (CO)(,8)((mu)(,3)-O)((mu)(,3)-(eta)('2)-CCHTol)((mu)-(eta)-CPh=CHPh). Reaction of 6 with","Made available in DSpace on 2014-12-15T23:18:49Z (GMT). No. of bitstreams: 1 8701460.pdf: 9009604 bytes, checksum: 13a29d4c95361f438afee271e03b4f34 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70509 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","239 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."],"dc:identifier":["http://hdl.handle.net/2142/70343","(UMI)AAI8701460"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Model Chemistry on Metal Surfaces: Synthesis, Structure and Reactivity Studies of Tungsten-Osmium Mixed-Metal Clusters"],"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"}