{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/39462"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/39462","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Oxidation addition of H-H bonds to iridium: developing novel active water soluble catalysts for hydrogenation of unsaturates","abstract":"The oxidative addition of H-H to iridium(l) trimethylphosphine complexes was studied and the reactivity of the resulting water soluble dihydrido iridium (III) complexes was investigated. One Dihydrido iridium(III) complex, mer-Ir(H)₂(PMe₃)₃CI <b>(2)</b> was characterized by ¹H, ³¹p and ¹³C NMR spectroscopy, CH analysis and single crystal xray diffraction. <b>(2)</b> reacted with the strong sigma donor PMe₃ to form [IrH2(PMe₃)4]CI <b>(3b)</b> without having to remove the chloride ligand. <b>(2)</b> reacted with monosubstituted acetylenes and an internal diyne in water to form the vinyl complexes Ir(H)(C(R')=C(H)-(R))(PMe₃)₃CI (R = CMe₃, C₆H₅, SiMe₃, R' = H, <b>(4)-(6);</b> R' = CCMe₃, R= Me, <b>(7)). (2)</b> also reacted in water with ethynylpyridine to form an unusual metallacycle \"trimer\" <b>(8)</b>. A mechanism for tltrimerizationtl is proposed. <b>(2)</b> also reacted with ethylene in water to form the diethyl iridium complex Ir(CH₂CH₃)₂(PMe₃)₃CI <b>(8)</b>. Encouraged by these results, catalytic hydrogenation of unsaturates in water was investigated. It was found that <b>(2)</b> is active as a water soluble catalyst for hydrogenation of unsaturates. A mechanism for catalytic hydrogenation was proposed.","abstract_html":"The oxidative addition of H-H to iridium(l) trimethylphosphine complexes was studied and the reactivity of the resulting water soluble dihydrido iridium (III) complexes was investigated. One Dihydrido iridium(III) complex, mer-Ir(H)₂(PMe₃)₃CI &lt;b&gt;(2)&lt;/b&gt; was characterized by ¹H, ³¹p and ¹³C NMR spectroscopy, CH analysis and single crystal xray diffraction. &lt;b&gt;(2)&lt;/b&gt; reacted with the strong sigma donor PMe₃ to form [IrH2(PMe₃)4]CI &lt;b&gt;(3b)&lt;/b&gt; without having to remove the chloride ligand. &lt;b&gt;(2)&lt;/b&gt; reacted with monosubstituted acetylenes and an internal diyne in water to form the vinyl complexes Ir(H)(C(R&#x27;)=C(H)-(R))(PMe₃)₃CI (R = CMe₃, C₆H₅, SiMe₃, R&#x27; = H, &lt;b&gt;(4)-(6);&lt;/b&gt; R&#x27; = CCMe₃, R= Me, &lt;b&gt;(7)). (2)&lt;/b&gt; also reacted in water with ethynylpyridine to form an unusual metallacycle &quot;trimer&quot; &lt;b&gt;(8)&lt;/b&gt;. A mechanism for tltrimerizationtl is proposed. &lt;b&gt;(2)&lt;/b&gt; also reacted with ethylene in water to form the diethyl iridium complex Ir(CH₂CH₃)₂(PMe₃)₃CI &lt;b&gt;(8)&lt;/b&gt;. Encouraged by these results, catalytic hydrogenation of unsaturates in water was investigated. It was found that &lt;b&gt;(2)&lt;/b&gt; is active as a water soluble catalyst for hydrogenation of unsaturates. A mechanism for catalytic hydrogenation was proposed.","abstract_has_math":false,"creators":["Le, Trang X."],"institution":"Virginia Tech","degree_name":"Ph. D.","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":["Merola, Joseph S."],"committee_members":["Hanson, Brian E.","Dillard, John G.","Tanko, James M.","Anderson, Mark R."],"year":1992,"date_issued":"1992-08-05","date_published":"1992-08-05","updated_at":"2026-07-22T22:19:15Z","subjects":[],"languages":["en"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-09232008-144717"],"render_values":[{"text":"etd-09232008-144717","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10919/39462","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.committeechair","label":"Committee Chair","values":["Merola, Joseph S."]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Hanson, Brian E.","Dillard, John G.","Tanko, James M.","Anderson, Mark R."]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Le, Trang X."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2014-03-14T21:19:14Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2014-03-14T21:19:14Z","2008-09-23"]},{"key":"dc:date.issued","label":"Date","values":["1992-08-05"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Tech"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","values":["Text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph. D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute and State University"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["etd-09232008-144717"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/39462"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The oxidative addition of H-H to iridium(l) trimethylphosphine complexes was studied and the reactivity of the resulting water soluble dihydrido iridium (III) complexes was investigated. One Dihydrido iridium(III) complex, mer-Ir(H)₂(PMe₃)₃CI <b>(2)</b> was characterized by ¹H, ³¹p and ¹³C NMR spectroscopy, CH analysis and single crystal xray diffraction. <b>(2)</b> reacted with the strong sigma donor PMe₃ to form [IrH2(PMe₃)4]CI <b>(3b)</b> without having to remove the chloride ligand. <b>(2)</b> reacted with monosubstituted acetylenes and an internal diyne in water to form the vinyl complexes Ir(H)(C(R')=C(H)-(R))(PMe₃)₃CI (R = CMe₃, C₆H₅, SiMe₃, R' = H, <b>(4)-(6);</b> R' = CCMe₃, R= Me, <b>(7)). (2)</b> also reacted in water with ethynylpyridine to form an unusual metallacycle \"trimer\" <b>(8)</b>. A mechanism for tltrimerizationtl is proposed. <b>(2)</b> also reacted with ethylene in water to form the diethyl iridium complex Ir(CH₂CH₃)₂(PMe₃)₃CI <b>(8)</b>. Encouraged by these results, catalytic hydrogenation of unsaturates in water was investigated. It was found that <b>(2)</b> is active as a water soluble catalyst for hydrogenation of unsaturates. A mechanism for catalytic hydrogenation was proposed."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph. D."]},{"key":"dc:format.medium","label":"Dc Format Medium","values":["BTD"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Oxidation addition of H-H bonds to iridium: developing novel active water soluble catalysts for hydrogenation of unsaturates"]}]}],"canonical_facts":{"dc:contributor.committeechair":["Merola, Joseph S."],"dc:contributor.committeemember":["Hanson, Brian E.","Dillard, John G.","Tanko, James M.","Anderson, Mark R."],"dc:contributor.department":["Chemistry"],"dc:creator":["Le, Trang X."],"dc:date.accessioned":["2014-03-14T21:19:14Z"],"dc:date.available":["2014-03-14T21:19:14Z","2008-09-23"],"dc:date.issued":["1992-08-05"],"dc:description.abstract":["The oxidative addition of H-H to iridium(l) trimethylphosphine complexes was studied and the reactivity of the resulting water soluble dihydrido iridium (III) complexes was investigated. One Dihydrido iridium(III) complex, mer-Ir(H)₂(PMe₃)₃CI <b>(2)</b> was characterized by ¹H, ³¹p and ¹³C NMR spectroscopy, CH analysis and single crystal xray diffraction. <b>(2)</b> reacted with the strong sigma donor PMe₃ to form [IrH2(PMe₃)4]CI <b>(3b)</b> without having to remove the chloride ligand. <b>(2)</b> reacted with monosubstituted acetylenes and an internal diyne in water to form the vinyl complexes Ir(H)(C(R')=C(H)-(R))(PMe₃)₃CI (R = CMe₃, C₆H₅, SiMe₃, R' = H, <b>(4)-(6);</b> R' = CCMe₃, R= Me, <b>(7)). (2)</b> also reacted in water with ethynylpyridine to form an unusual metallacycle \"trimer\" <b>(8)</b>. A mechanism for tltrimerizationtl is proposed. <b>(2)</b> also reacted with ethylene in water to form the diethyl iridium complex Ir(CH₂CH₃)₂(PMe₃)₃CI <b>(8)</b>. Encouraged by these results, catalytic hydrogenation of unsaturates in water was investigated. It was found that <b>(2)</b> is active as a water soluble catalyst for hydrogenation of unsaturates. A mechanism for catalytic hydrogenation was proposed."],"dc:description.degree":["Ph. D."],"dc:format.medium":["BTD"],"dc:format.mimetype":["application/pdf"],"dc:identifier.other":["etd-09232008-144717"],"dc:identifier.uri":["http://hdl.handle.net/10919/39462"],"dc:language.iso":["en"],"dc:publisher":["Virginia Tech"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:title":["Oxidation addition of H-H bonds to iridium: developing novel active water soluble catalysts for hydrogenation of unsaturates"],"dc:type":["Dissertation"],"dc:type.dcmitype":["Text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Ph. D."],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-22T22:19:15Z"}