{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/67219"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/67219","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Base Catalysis of Ligand Substitution in Metal Carbonyls","abstract":"Manganese(I) carbonyls can undergo substitution by a variety of mechanisms. Three different mechanisms have been found for the substitution reactions of Mn(CO)(,5)CH(,3)CN('+).","abstract_html":"Manganese(I) carbonyls can undergo substitution by a variety of mechanisms. Three different mechanisms have been found for the substitution reactions of Mn(CO)(,5)CH(,3)CN('+).","abstract_has_math":false,"creators":["Bellus, Peter Alexander"],"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":"2014-12-13T20:10:52Z","date_published":"2014-12-13T20:10:52Z","updated_at":"2026-07-22T22:25:57Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8017915"],"render_values":[{"text":"(UMI)AAI8017915","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/67219","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Bellus, Peter Alexander"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-13T20:10:52Z","10000-01-01","1980"]},{"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/2142/67219","(UMI)AAI8017915"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Manganese(I) carbonyls can undergo substitution by a variety of mechanisms. Three different mechanisms have been found for the substitution reactions of Mn(CO)(,5)CH(,3)CN('+).","Mn(CO)(,5)CH(,3)CN('+) reacts with P(C(,6)H(,5))(,3) in CH(,3)CN by a dissociative process. CH(,3)CN dissociates and P(C(,6)H(,5))(,3) takes its place to form Mn(CO(,5))P(C(,6)H(,5))(,3)('+). First order overall, and first order in metal carbonyl, kinetics are observed.","Mn(CO)(,5)CH(,3)CN('+) reacts with pyridine in CH(,3)CN by an associative process that is best explained by a carbonyl base-attack mechanism, whereby a pyridine attacks the carbon of a CO to generate an adduct-ligand of the formula, ('-)C(O)NC(,5)H(,5). This adduct ligand labilizes the complex toward loss of the ligands cis to it. Pyridine or CH(,3)CN can fill the vacancy thus generated. The substitution process continues until the adduct-ligand breaks up, regenerating free pyridine and a coordinated CO, in the observed product, Mn(CO)(,3)(CH(,3)CN) (pyridine)(,2)('+). The kinetics observed are second order overall and first order each in metal carbonyl and pyridine.","Mn(CO)(,5)CH(,3)CN('+) reacts with pyridine in CH(,3)NO(,2) also by a base-attack mechanism. The nucleophile is CH(,2)NO(,2)('-), formed by the deprotonation of CH(,3)NO(,2) by pyridine. The adduct-ligand formed is C(O)ON(O)CH(,2), which labilizes the complex towards loss of ligand cis to it, and substitution occurs. The adduct ligand breaks down to give CO(,2) and, presumably, CH(,2)NO('-). Mn(CO)(,3)(pyridine)(,3)('+) is the metal containing product. The kinetics show first order dependences on both the metal carbonyl and pyridine, and an inverse dependence on pyridinium ion.","Mn(CO)(,5)CH(,3)CN('+) also undergoes a complex series of reactions in CH(,3)CN containing both pyridine and water. Mn(O) binuclear species, Mn(CO)(,5)('-), Mn(II) species and Mn(I) carbonyls are among the products. Formation of a hydroxycarbonyl species is thought to be the key step, leading to substitution by virtue of the cis-labilizing ability of the COOH moiety, and leading to Mn(CO)(,5)('-) formation via the hydroxycarbonyl. Electron transfer steps involving these species generate Mn(O) radicals and Mn(II).","The application of the base-attack mechanism of ligand substitution to other metal carbonyl systems is discussed.","Made available in DSpace on 2014-12-13T20:10:52Z (GMT). No. of bitstreams: 1 8017915.pdf: 4985243 bytes, checksum: 2f1a885b5beac8c7811853e970d62ae3 (MD5) Previous issue date: 1980","Embargo set by: Seth Robbins for item 67397 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","233 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1980."]},{"key":"dc:title","label":"Title","values":["Base Catalysis of Ligand Substitution in Metal Carbonyls"]}]}],"canonical_facts":{"dc:creator":["Bellus, Peter Alexander"],"dc:date":["2014-12-13T20:10:52Z","10000-01-01","1980"],"dc:description":["Manganese(I) carbonyls can undergo substitution by a variety of mechanisms. Three different mechanisms have been found for the substitution reactions of Mn(CO)(,5)CH(,3)CN('+).","Mn(CO)(,5)CH(,3)CN('+) reacts with P(C(,6)H(,5))(,3) in CH(,3)CN by a dissociative process. CH(,3)CN dissociates and P(C(,6)H(,5))(,3) takes its place to form Mn(CO(,5))P(C(,6)H(,5))(,3)('+). First order overall, and first order in metal carbonyl, kinetics are observed.","Mn(CO)(,5)CH(,3)CN('+) reacts with pyridine in CH(,3)CN by an associative process that is best explained by a carbonyl base-attack mechanism, whereby a pyridine attacks the carbon of a CO to generate an adduct-ligand of the formula, ('-)C(O)NC(,5)H(,5). This adduct ligand labilizes the complex toward loss of the ligands cis to it. Pyridine or CH(,3)CN can fill the vacancy thus generated. The substitution process continues until the adduct-ligand breaks up, regenerating free pyridine and a coordinated CO, in the observed product, Mn(CO)(,3)(CH(,3)CN) (pyridine)(,2)('+). The kinetics observed are second order overall and first order each in metal carbonyl and pyridine.","Mn(CO)(,5)CH(,3)CN('+) reacts with pyridine in CH(,3)NO(,2) also by a base-attack mechanism. The nucleophile is CH(,2)NO(,2)('-), formed by the deprotonation of CH(,3)NO(,2) by pyridine. The adduct-ligand formed is C(O)ON(O)CH(,2), which labilizes the complex towards loss of ligand cis to it, and substitution occurs. The adduct ligand breaks down to give CO(,2) and, presumably, CH(,2)NO('-). Mn(CO)(,3)(pyridine)(,3)('+) is the metal containing product. The kinetics show first order dependences on both the metal carbonyl and pyridine, and an inverse dependence on pyridinium ion.","Mn(CO)(,5)CH(,3)CN('+) also undergoes a complex series of reactions in CH(,3)CN containing both pyridine and water. Mn(O) binuclear species, Mn(CO)(,5)('-), Mn(II) species and Mn(I) carbonyls are among the products. Formation of a hydroxycarbonyl species is thought to be the key step, leading to substitution by virtue of the cis-labilizing ability of the COOH moiety, and leading to Mn(CO)(,5)('-) formation via the hydroxycarbonyl. Electron transfer steps involving these species generate Mn(O) radicals and Mn(II).","The application of the base-attack mechanism of ligand substitution to other metal carbonyl systems is discussed.","Made available in DSpace on 2014-12-13T20:10:52Z (GMT). No. of bitstreams: 1 8017915.pdf: 4985243 bytes, checksum: 2f1a885b5beac8c7811853e970d62ae3 (MD5) Previous issue date: 1980","Embargo set by: Seth Robbins for item 67397 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","233 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1980."],"dc:identifier":["http://hdl.handle.net/2142/67219","(UMI)AAI8017915"],"dc:language":["eng"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Base Catalysis of Ligand Substitution in Metal Carbonyls"],"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":"2026-07-22T22:25:57Z"}