{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/22666"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/22666","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Competing reaction pathways in the photochemical reactions of metal carbonyl compounds","abstract":"The photochemical reaction of Mn$\\sb2$(CO)$\\sb{10}$ with HSnBu$\\sb3$ has been studied by continuous photolysis. Sunlamp irradiation of a CO-saturated hexane solution of Mn$\\sb2$(CO)$\\sb{10}$ and HSnBu$\\sb3$ results in formation of HMn(CO)$\\sb5$ and Bu$\\sb3$SnMn(CO)$\\sb5$ in equimolar quantities. The rate of disappearance of Mn$\\sb2$(CO)$\\sb{10}$ and formation of products exhibit an inverse (CO) dependence.","abstract_html":"The photochemical reaction of Mn$\\sb2$(CO)$\\sb{10}$ with HSnBu$\\sb3$ has been studied by continuous photolysis. Sunlamp irradiation of a CO-saturated hexane solution of Mn$\\sb2$(CO)$\\sb{10}$ and HSnBu$\\sb3$ results in formation of HMn(CO)$\\sb5$ and Bu$\\sb3$SnMn(CO)$\\sb5$ in equimolar quantities. The rate of disappearance of Mn$\\sb2$(CO)$\\sb{10}$ and formation of products exhibit an inverse (CO) dependence.","abstract_has_math":true,"creators":["Sullivan, Richard Joseph"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Brown, Theodore L."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:47:22Z","date_published":"2011-05-07T13:47:22Z","updated_at":"2026-07-22T22:25:20Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1990 Sullivan, Richard Joseph"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114428","(UMI)AAI9114428"],"render_values":[{"text":"AAI9114428","href":null,"code":true},{"text":"(UMI)AAI9114428","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/22666","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Brown, Theodore L."]},{"key":"dc:creator","label":"Author","values":["Sullivan, Richard Joseph"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:47:22Z","10000-01-01","1990"]},{"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"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1990 Sullivan, Richard Joseph"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9114428","(UMI)AAI9114428","http://hdl.handle.net/2142/22666"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The photochemical reaction of Mn$\\sb2$(CO)$\\sb{10}$ with HSnBu$\\sb3$ has been studied by continuous photolysis. Sunlamp irradiation of a CO-saturated hexane solution of Mn$\\sb2$(CO)$\\sb{10}$ and HSnBu$\\sb3$ results in formation of HMn(CO)$\\sb5$ and Bu$\\sb3$SnMn(CO)$\\sb5$ in equimolar quantities. The rate of disappearance of Mn$\\sb2$(CO)$\\sb{10}$ and formation of products exhibit an inverse (CO) dependence.","When the reaction of Mn$\\sb2$(CO)$\\sb{10}$ with HSnBu$\\sb3$ is performed under 1 atm AR, the rate of disappearance of Mn$\\sb2$(CO)$\\sb{10}$ is much faster than when CO is present, HMn(CO)$\\sb5$ forms in much greater quantities than Bu$\\sb3$SnMn(CO)$\\sb5$, and a third product, identified as HMn(CO)$\\sb4$(SnBu$\\sb3$)$\\sb2$, forms as the other major product. The above observations are consistent with a mechanism involving oxidative addition of HSnBu$\\sb3$ to Mn$\\sb2$(CO)$\\sb9$.","The reactions of HSnBu$\\sb3$ with Mn(CO)$\\sb4$L$\\cdot$ (L = CO or PR$\\sb3$) and Mn$\\sb2$(CO)$\\sb7$L$\\sb2$ were studied by flash photolysis. In every case examined, HSnBu$\\sb3$ undergoes oxidative addition with Mn$\\sb2$(CO)$\\sb7$L$\\sb2$. However, H-atom transfer to Mn(CO)$\\sb4$L$\\cdot$ does not occur. For L = CO, PMe$\\sb3$, P(i-Bu)$\\sb3$, and P(O-i-Pr)$\\sb3$, the initial product of oxidative addition, Mn$\\sb2$(CO)$\\sb7$L$\\sb2$(H)(SnBu$\\sb3$), is observed. At longer time intervals, this intermediate disappears by reductive elimination of HMn(CO)$\\sb4$L. Mn$\\sb2$(CO)$\\sb7$L$\\sb2$(H)(SnBu$\\sb3$) is not observed when the metal center is crowded as in the cases of L = P(i-Pr)$\\sb3$ and P(C$\\sb6$H$\\sb{11}$)$\\sb3$ because oxidative addition is slow relative to reductive elimination.","The transient absorbance decay of Mn$\\sb2$(CO)$\\sb7$L$\\sb2$ in the presence of HSnBu$\\sb3$ obeys pseudo-first-order kinetics. Plots of K$\\sb{\\rm obs}$ vs. (HSnBu$\\sb3$) are linear for L = P(i-Bu)$\\sb3$, P(i-Pr)$\\sb3$, and P(C$\\sb6$H$\\sb{11}$)$\\sb3$. However, for L = PMe$\\sb3$ and P(n-Bu)$\\sb3$, the k$\\sb{\\rm obs}$ vs (HSnBu$\\sb3$) plot is non-linear throughout the entire (HSnBu$\\sb3$) range. A mechanism involving a rate determining equilibrium between unbridged Mn$\\sb2$(CO)$\\sb7$L$\\sb2$ and semi-bridged Mn$\\sb2$(CO)$\\sb7$L$\\sb2$ prior to oxidative addition of HSnBu$\\sb3$ accounts for the experimental observations.","Made available in DSpace on 2011-05-07T13:47:22Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114428.pdf: 11197806 bytes, checksum: 4577d82bec60f83727c381a40de0f3a9 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:59:11Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:27:53-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Competing reaction pathways in the photochemical reactions of metal carbonyl compounds"]}]}],"canonical_facts":{"dc:contributor":["Brown, Theodore L."],"dc:creator":["Sullivan, Richard Joseph"],"dc:date":["2011-05-07T13:47:22Z","10000-01-01","1990"],"dc:description":["The photochemical reaction of Mn$\\sb2$(CO)$\\sb{10}$ with HSnBu$\\sb3$ has been studied by continuous photolysis. Sunlamp irradiation of a CO-saturated hexane solution of Mn$\\sb2$(CO)$\\sb{10}$ and HSnBu$\\sb3$ results in formation of HMn(CO)$\\sb5$ and Bu$\\sb3$SnMn(CO)$\\sb5$ in equimolar quantities. The rate of disappearance of Mn$\\sb2$(CO)$\\sb{10}$ and formation of products exhibit an inverse (CO) dependence.","When the reaction of Mn$\\sb2$(CO)$\\sb{10}$ with HSnBu$\\sb3$ is performed under 1 atm AR, the rate of disappearance of Mn$\\sb2$(CO)$\\sb{10}$ is much faster than when CO is present, HMn(CO)$\\sb5$ forms in much greater quantities than Bu$\\sb3$SnMn(CO)$\\sb5$, and a third product, identified as HMn(CO)$\\sb4$(SnBu$\\sb3$)$\\sb2$, forms as the other major product. The above observations are consistent with a mechanism involving oxidative addition of HSnBu$\\sb3$ to Mn$\\sb2$(CO)$\\sb9$.","The reactions of HSnBu$\\sb3$ with Mn(CO)$\\sb4$L$\\cdot$ (L = CO or PR$\\sb3$) and Mn$\\sb2$(CO)$\\sb7$L$\\sb2$ were studied by flash photolysis. In every case examined, HSnBu$\\sb3$ undergoes oxidative addition with Mn$\\sb2$(CO)$\\sb7$L$\\sb2$. However, H-atom transfer to Mn(CO)$\\sb4$L$\\cdot$ does not occur. For L = CO, PMe$\\sb3$, P(i-Bu)$\\sb3$, and P(O-i-Pr)$\\sb3$, the initial product of oxidative addition, Mn$\\sb2$(CO)$\\sb7$L$\\sb2$(H)(SnBu$\\sb3$), is observed. At longer time intervals, this intermediate disappears by reductive elimination of HMn(CO)$\\sb4$L. Mn$\\sb2$(CO)$\\sb7$L$\\sb2$(H)(SnBu$\\sb3$) is not observed when the metal center is crowded as in the cases of L = P(i-Pr)$\\sb3$ and P(C$\\sb6$H$\\sb{11}$)$\\sb3$ because oxidative addition is slow relative to reductive elimination.","The transient absorbance decay of Mn$\\sb2$(CO)$\\sb7$L$\\sb2$ in the presence of HSnBu$\\sb3$ obeys pseudo-first-order kinetics. Plots of K$\\sb{\\rm obs}$ vs. (HSnBu$\\sb3$) are linear for L = P(i-Bu)$\\sb3$, P(i-Pr)$\\sb3$, and P(C$\\sb6$H$\\sb{11}$)$\\sb3$. However, for L = PMe$\\sb3$ and P(n-Bu)$\\sb3$, the k$\\sb{\\rm obs}$ vs (HSnBu$\\sb3$) plot is non-linear throughout the entire (HSnBu$\\sb3$) range. A mechanism involving a rate determining equilibrium between unbridged Mn$\\sb2$(CO)$\\sb7$L$\\sb2$ and semi-bridged Mn$\\sb2$(CO)$\\sb7$L$\\sb2$ prior to oxidative addition of HSnBu$\\sb3$ accounts for the experimental observations.","Made available in DSpace on 2011-05-07T13:47:22Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9114428.pdf: 11197806 bytes, checksum: 4577d82bec60f83727c381a40de0f3a9 (MD5) Previous issue date: 1990","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:59:11Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:27:53-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9114428","(UMI)AAI9114428","http://hdl.handle.net/2142/22666"],"dc:language":["eng"],"dc:rights":["Copyright 1990 Sullivan, Richard Joseph"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Competing reaction pathways in the photochemical reactions of metal carbonyl 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":"2026-07-22T22:25:20Z"}