{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70202"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70202","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Mechanistic Studies of Rhodium Oxidation Catalysts","abstract":"Over the past eight years a number of catalytic processes for the O(,2) oxidation of terminal olefins have been proposed to proceed through non-free radical, non-Wacker mechanisms involving the coordination of O(,2) and olefin to a rhodium(I) catalyst. One particularly promising system is the Rh/Cu co-catalyzed O(,2) oxidation of terminal olefins to almost exclusively 2-hexanone. The relatively short lifetimes of the homogeneous catalysts for this olefin oxidation encouraged us to seek a functionalized solid support to site-isolate the rhodium complexes. This approach is based on the assumption that the catalyst deactivation process is multi-ordered in rhodium. In chapter 2 is described the immobilization of {Rh(CO)(,2)S'(,n)}BF(,4) using a silica gel bound organosulfide ligand, {SG}-SH. When solid supports possessing site-isolated sulfide are employed, the monomeric rhodium carbonyl complexes, {SG}-SRh(CO)(,2)S'(,n), are formed. These produce catalysts for the oxidation of 1-hexene to 2-hexanone, and are more stable to deactivation than the analogous homogeneous reaction using {Rh(CO)(,2)S'(,n)}BF(,4). The O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) was studied as part of an investigation to determine the character of the catalyst for the homogeneous Rh/Cu co-catalyzed oxidation of 1-hexene. In chapter 3 are presented the result of a detailed investigation of the mechanism of the O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) to RhCl(,3)(H(,2)O)(,2)CH(,3)CH(,2)OH. This has been found to proceed by an unusual process involving the coordination of in situ generated HOOH to {Rh(CO)(,2)Cl}(,2), forming H(,2){Rh(CO)Cl(,2)(OOH)} as a stable intermediate. The observations that the O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) produces rhodium(III) trichloride, and that this process corresponds to the initiation of the O(,2) oxidation of 1-hexene to 2-hexanone, has led to the characterization of the catalyst for the Rh/Cu co-catalyzed oxidation of 1-hexene at 40.C as RhCl(,2)S'(,4)('+). These results, and a general investigation of the mechanism of this catalytic 1-hexene oxidation, are presented in chapter 4. It has been found that RhCl(,3) 3 H(,2)O catalyzes the HOOH oxidation of 1-hexene to 2-hexanone, indicating peroxide is the direct oxidant in this system. Mechanisms for the Rh-only and Rh/Cu co-catalyzed oxidations of 1-hexene are proposed which are consistant with both the earlier reported results, and those presented in this study.","abstract_html":"Over the past eight years a number of catalytic processes for the O(,2) oxidation of terminal olefins have been proposed to proceed through non-free radical, non-Wacker mechanisms involving the coordination of O(,2) and olefin to a rhodium(I) catalyst. One particularly promising system is the Rh/Cu co-catalyzed O(,2) oxidation of terminal olefins to almost exclusively 2-hexanone. The relatively short lifetimes of the homogeneous catalysts for this olefin oxidation encouraged us to seek a functionalized solid support to site-isolate the rhodium complexes. This approach is based on the assumption that the catalyst deactivation process is multi-ordered in rhodium. In chapter 2 is described the immobilization of {Rh(CO)(,2)S'(,n)}BF(,4) using a silica gel bound organosulfide ligand, {SG}-SH. When solid supports possessing site-isolated sulfide are employed, the monomeric rhodium carbonyl complexes, {SG}-SRh(CO)(,2)S'(,n), are formed. These produce catalysts for the oxidation of 1-hexene to 2-hexanone, and are more stable to deactivation than the analogous homogeneous reaction using {Rh(CO)(,2)S'(,n)}BF(,4). The O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) was studied as part of an investigation to determine the character of the catalyst for the homogeneous Rh/Cu co-catalyzed oxidation of 1-hexene. In chapter 3 are presented the result of a detailed investigation of the mechanism of the O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) to RhCl(,3)(H(,2)O)(,2)CH(,3)CH(,2)OH. This has been found to proceed by an unusual process involving the coordination of in situ generated HOOH to {Rh(CO)(,2)Cl}(,2), forming H(,2){Rh(CO)Cl(,2)(OOH)} as a stable intermediate. The observations that the O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) produces rhodium(III) trichloride, and that this process corresponds to the initiation of the O(,2) oxidation of 1-hexene to 2-hexanone, has led to the characterization of the catalyst for the Rh/Cu co-catalyzed oxidation of 1-hexene at 40.C as RhCl(,2)S'(,4)('+). These results, and a general investigation of the mechanism of this catalytic 1-hexene oxidation, are presented in chapter 4. It has been found that RhCl(,3) 3 H(,2)O catalyzes the HOOH oxidation of 1-hexene to 2-hexanone, indicating peroxide is the direct oxidant in this system. Mechanisms for the Rh-only and Rh/Cu co-catalyzed oxidations of 1-hexene are proposed which are consistant with both the earlier reported results, and those presented in this study.","abstract_has_math":false,"creators":["Nyberg, Eric David"],"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":"2014-12-15T23:17:48Z","date_published":"2014-12-15T23:17:48Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8302944"],"render_values":[{"text":"(UMI)AAI8302944","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70202","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Nyberg, Eric David"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:17:48Z","10000-01-01","1982"]},{"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/2142/70202","(UMI)AAI8302944"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Over the past eight years a number of catalytic processes for the O(,2) oxidation of terminal olefins have been proposed to proceed through non-free radical, non-Wacker mechanisms involving the coordination of O(,2) and olefin to a rhodium(I) catalyst. One particularly promising system is the Rh/Cu co-catalyzed O(,2) oxidation of terminal olefins to almost exclusively 2-hexanone. The relatively short lifetimes of the homogeneous catalysts for this olefin oxidation encouraged us to seek a functionalized solid support to site-isolate the rhodium complexes. This approach is based on the assumption that the catalyst deactivation process is multi-ordered in rhodium. In chapter 2 is described the immobilization of {Rh(CO)(,2)S'(,n)}BF(,4) using a silica gel bound organosulfide ligand, {SG}-SH. When solid supports possessing site-isolated sulfide are employed, the monomeric rhodium carbonyl complexes, {SG}-SRh(CO)(,2)S'(,n), are formed. These produce catalysts for the oxidation of 1-hexene to 2-hexanone, and are more stable to deactivation than the analogous homogeneous reaction using {Rh(CO)(,2)S'(,n)}BF(,4). The O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) was studied as part of an investigation to determine the character of the catalyst for the homogeneous Rh/Cu co-catalyzed oxidation of 1-hexene. In chapter 3 are presented the result of a detailed investigation of the mechanism of the O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) to RhCl(,3)(H(,2)O)(,2)CH(,3)CH(,2)OH. This has been found to proceed by an unusual process involving the coordination of in situ generated HOOH to {Rh(CO)(,2)Cl}(,2), forming H(,2){Rh(CO)Cl(,2)(OOH)} as a stable intermediate. The observations that the O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) produces rhodium(III) trichloride, and that this process corresponds to the initiation of the O(,2) oxidation of 1-hexene to 2-hexanone, has led to the characterization of the catalyst for the Rh/Cu co-catalyzed oxidation of 1-hexene at 40.C as RhCl(,2)S'(,4)('+). These results, and a general investigation of the mechanism of this catalytic 1-hexene oxidation, are presented in chapter 4. It has been found that RhCl(,3) 3 H(,2)O catalyzes the HOOH oxidation of 1-hexene to 2-hexanone, indicating peroxide is the direct oxidant in this system. Mechanisms for the Rh-only and Rh/Cu co-catalyzed oxidations of 1-hexene are proposed which are consistant with both the earlier reported results, and those presented in this study.","Made available in DSpace on 2014-12-15T23:17:48Z (GMT). No. of bitstreams: 1 8302944.pdf: 6318134 bytes, checksum: 8d21bedace58c4a04624ba943ac6957d (MD5) Previous issue date: 1982","Embargo set by: Seth Robbins for item 70368 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","215 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1982."]},{"key":"dc:title","label":"Title","values":["Mechanistic Studies of Rhodium Oxidation Catalysts"]}]}],"canonical_facts":{"dc:creator":["Nyberg, Eric David"],"dc:date":["2014-12-15T23:17:48Z","10000-01-01","1982"],"dc:description":["Over the past eight years a number of catalytic processes for the O(,2) oxidation of terminal olefins have been proposed to proceed through non-free radical, non-Wacker mechanisms involving the coordination of O(,2) and olefin to a rhodium(I) catalyst. One particularly promising system is the Rh/Cu co-catalyzed O(,2) oxidation of terminal olefins to almost exclusively 2-hexanone. The relatively short lifetimes of the homogeneous catalysts for this olefin oxidation encouraged us to seek a functionalized solid support to site-isolate the rhodium complexes. This approach is based on the assumption that the catalyst deactivation process is multi-ordered in rhodium. In chapter 2 is described the immobilization of {Rh(CO)(,2)S'(,n)}BF(,4) using a silica gel bound organosulfide ligand, {SG}-SH. When solid supports possessing site-isolated sulfide are employed, the monomeric rhodium carbonyl complexes, {SG}-SRh(CO)(,2)S'(,n), are formed. These produce catalysts for the oxidation of 1-hexene to 2-hexanone, and are more stable to deactivation than the analogous homogeneous reaction using {Rh(CO)(,2)S'(,n)}BF(,4). The O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) was studied as part of an investigation to determine the character of the catalyst for the homogeneous Rh/Cu co-catalyzed oxidation of 1-hexene. In chapter 3 are presented the result of a detailed investigation of the mechanism of the O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) to RhCl(,3)(H(,2)O)(,2)CH(,3)CH(,2)OH. This has been found to proceed by an unusual process involving the coordination of in situ generated HOOH to {Rh(CO)(,2)Cl}(,2), forming H(,2){Rh(CO)Cl(,2)(OOH)} as a stable intermediate. The observations that the O(,2) oxidation of {Rh(CO)(,2)Cl}(,2) produces rhodium(III) trichloride, and that this process corresponds to the initiation of the O(,2) oxidation of 1-hexene to 2-hexanone, has led to the characterization of the catalyst for the Rh/Cu co-catalyzed oxidation of 1-hexene at 40.C as RhCl(,2)S'(,4)('+). These results, and a general investigation of the mechanism of this catalytic 1-hexene oxidation, are presented in chapter 4. It has been found that RhCl(,3) 3 H(,2)O catalyzes the HOOH oxidation of 1-hexene to 2-hexanone, indicating peroxide is the direct oxidant in this system. Mechanisms for the Rh-only and Rh/Cu co-catalyzed oxidations of 1-hexene are proposed which are consistant with both the earlier reported results, and those presented in this study.","Made available in DSpace on 2014-12-15T23:17:48Z (GMT). No. of bitstreams: 1 8302944.pdf: 6318134 bytes, checksum: 8d21bedace58c4a04624ba943ac6957d (MD5) Previous issue date: 1982","Embargo set by: Seth Robbins for item 70368 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","215 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1982."],"dc:identifier":["http://hdl.handle.net/2142/70202","(UMI)AAI8302944"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Mechanistic Studies of Rhodium Oxidation Catalysts"],"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"}