{"id":{"repo_id":"unt","oai_identifier":"info:ark/67531/metadc2665"},"canonical_url":"https://search.dev.ndltd.org/etd/unt/info:ark/67531/metadc2665","repository":{"repo_id":"unt","name":"University of North Texas","base_url":"https://digital.library.unt.edu/oai/"},"display":{"title":"Diphosphine Ligand Activation Studies with Organotransition-Metal Compounds","abstract":"Thermolysis of CoRu(CO)7(m -PPh2) (1) in refluxing 1,2-dichloroethane in the presence of the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the new mixed-metal complexes CoRu(CO)4(μ -P-P)(μ -PPh2) [where P-P = bma (3); bpcd (6)], along with trace amounts of the known complex CoRu(CO)6(PPh3)(μ -PPh2) (4). The requisite pentacarbonyl intermediates CoRu(CO)5(μ -P-P)(μ -PPh2) [where P-P = bma (2); bpcd (5)] have been prepared by separate routes and studied for their conversion to CoRu(CO)4(μ -P-P)(μ -PPh2). The complexes 2/3 and 5/6 have been isolated and fully characterized in solution by IR and NMR spectroscopy. The kinetics for the conversion of 2→3 and of 5→6 were measured by IR spectroscopy in chlorobenzene solvent. On the basis of the first-order rate constants, CO inhibition, and the activation parameters, a mechanism involving dissociative CO loss as the rate-limiting step is proposed. The solid-state structure of CoRu(CO)4(μ -bma)(μ -PPh2) (3) reveals that the two PPh2 groups are bound to the ruthenium center while the maleic anhydride π bond is coordinated to the cobalt atom. Thermolysis of the cluster Ru3(CO)12 with the bis(phosphine)hydrazine ligand (MeO)2PN(Me)N(Me)P(OMe)2 (dmpdmh) in toluene at 75°C furnishes the known clusters Ru4(CO)12[μ -N(Me)N(Me)] (9) and Ru3(CO)11[P(OMe)3] (10), in addition to the new cluster Ru3(CO)10(dmpdmh) (8) and the phosphite-tethered cluster Ru3(CO)9[μ -P(OMe)3] (11). The simple substitution product Ru3(CO)10(dmpdmh), a logical intermediate to clusters 9-11, was synthesized by treating Ru3(CO)12 and dmpdmh with Me3NO in CH2Cl2 at room temperature, and independent thermolysis reactions using cluster 8 were shown to yield clusters 9-11. The tetrahedrane cluster FeCo2(CO)9(μ3-S) reacts with the redox-active ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) to give the disubstituted cluster FeCo2(CO)7(bpcd)(μ3-S) as the sole product. This diphosphine-substituted cluster contains a cobalt-bound, chelating bpcd ligand. The solid-state structure has been unequivocally established by X-ray diffraction analysis. Cyclic voltammetric studies on FeCo2(CO)7(bpcd)(μ3-S) reveal the presence of two quasireversible redox responses assigned to the 0/1- and 1-/2- redox couples. The orbital composition of these redox couples has been examined by carrying out extended Hückel MO calculations on the model complex FeCo2(CO)7(H4-bpcd)(μ3-S), with the results being compared to related cluster compounds.","abstract_html":"Thermolysis of CoRu(CO)7(m -PPh2) (1) in refluxing 1,2-dichloroethane in the presence of the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the new mixed-metal complexes CoRu(CO)4(μ -P-P)(μ -PPh2) [where P-P = bma (3); bpcd (6)], along with trace amounts of the known complex CoRu(CO)6(PPh3)(μ -PPh2) (4). The requisite pentacarbonyl intermediates CoRu(CO)5(μ -P-P)(μ -PPh2) [where P-P = bma (2); bpcd (5)] have been prepared by separate routes and studied for their conversion to CoRu(CO)4(μ -P-P)(μ -PPh2). The complexes 2/3 and 5/6 have been isolated and fully characterized in solution by IR and NMR spectroscopy. The kinetics for the conversion of 2→3 and of 5→6 were measured by IR spectroscopy in chlorobenzene solvent. On the basis of the first-order rate constants, CO inhibition, and the activation parameters, a mechanism involving dissociative CO loss as the rate-limiting step is proposed. The solid-state structure of CoRu(CO)4(μ -bma)(μ -PPh2) (3) reveals that the two PPh2 groups are bound to the ruthenium center while the maleic anhydride π bond is coordinated to the cobalt atom. Thermolysis of the cluster Ru3(CO)12 with the bis(phosphine)hydrazine ligand (MeO)2PN(Me)N(Me)P(OMe)2 (dmpdmh) in toluene at 75°C furnishes the known clusters Ru4(CO)12[μ -N(Me)N(Me)] (9) and Ru3(CO)11[P(OMe)3] (10), in addition to the new cluster Ru3(CO)10(dmpdmh) (8) and the phosphite-tethered cluster Ru3(CO)9[μ -P(OMe)3] (11). The simple substitution product Ru3(CO)10(dmpdmh), a logical intermediate to clusters 9-11, was synthesized by treating Ru3(CO)12 and dmpdmh with Me3NO in CH2Cl2 at room temperature, and independent thermolysis reactions using cluster 8 were shown to yield clusters 9-11. The tetrahedrane cluster FeCo2(CO)9(μ3-S) reacts with the redox-active ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) to give the disubstituted cluster FeCo2(CO)7(bpcd)(μ3-S) as the sole product. This diphosphine-substituted cluster contains a cobalt-bound, chelating bpcd ligand. The solid-state structure has been unequivocally established by X-ray diffraction analysis. Cyclic voltammetric studies on FeCo2(CO)7(bpcd)(μ3-S) reveal the presence of two quasireversible redox responses assigned to the 0/1- and 1-/2- redox couples. The orbital composition of these redox couples has been examined by carrying out extended Hückel MO calculations on the model complex FeCo2(CO)7(H4-bpcd)(μ3-S), with the results being compared to related cluster compounds.","abstract_has_math":false,"creators":["Wang, Jiancheng"],"institution":"University of North Texas","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Richmond, Michael","Schwartz, Martin","Golden, Teresa D.","Wiedenfeld, David"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2000,"date_issued":"2000-12","date_published":"2000-12","updated_at":"2026-07-24T05:34:52Z","subjects":["Ligands.","Organotransition metal compounds.","CoRu(CO)4(μ -P-P)(μ -PPh2)","Ru3(CO)10(dmpdmh)","thermolysis","diphosphine ligands","new mixed-metalcomplexes"],"languages":["English"],"rights":["Use restricted to UNT Community","Copyright","Wang, Jiancheng","Copyright is held by the author, unless otherwise noted. All rights reserved."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["oclc: 47785437","https://digital.library.unt.edu/ark:/67531/metadc2665/","ark: ark:/67531/metadc2665"],"render_values":[{"text":"oclc: 47785437","href":null,"code":true},{"text":"https://digital.library.unt.edu/ark:/67531/metadc2665/","href":"https://digital.library.unt.edu/ark:/67531/metadc2665/","code":true},{"text":"ark: ark:/67531/metadc2665","href":null,"code":true}]}]},"links":{"outbound_url":"https://doi.org/10.12794/metadc2665","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Richmond, Michael","Schwartz, Martin","Golden, Teresa D.","Wiedenfeld, David"]},{"key":"dc:creator","label":"Author","values":["Wang, Jiancheng"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2000-12"]},{"key":"dc:publisher","label":"Institution","values":["University of North Texas"]},{"key":"dc:type","label":"Dc Type","values":["Thesis or Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Ligands.","Organotransition metal compounds.","CoRu(CO)4(μ -P-P)(μ -PPh2)","Ru3(CO)10(dmpdmh)","thermolysis","diphosphine ligands","new mixed-metalcomplexes"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]},{"key":"dc:rights","label":"Dc Rights","values":["Use restricted to UNT Community","Copyright","Wang, Jiancheng","Copyright is held by the author, unless otherwise noted. All rights reserved."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["oclc: 47785437","doi: 10.12794/metadc2665","https://digital.library.unt.edu/ark:/67531/metadc2665/","ark: ark:/67531/metadc2665"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Thermolysis of CoRu(CO)7(m -PPh2) (1) in refluxing 1,2-dichloroethane in the presence of the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the new mixed-metal complexes CoRu(CO)4(μ -P-P)(μ -PPh2) [where P-P = bma (3); bpcd (6)], along with trace amounts of the known complex CoRu(CO)6(PPh3)(μ -PPh2) (4). The requisite pentacarbonyl intermediates CoRu(CO)5(μ -P-P)(μ -PPh2) [where P-P = bma (2); bpcd (5)] have been prepared by separate routes and studied for their conversion to CoRu(CO)4(μ -P-P)(μ -PPh2). The complexes 2/3 and 5/6 have been isolated and fully characterized in solution by IR and NMR spectroscopy. The kinetics for the conversion of 2→3 and of 5→6 were measured by IR spectroscopy in chlorobenzene solvent. On the basis of the first-order rate constants, CO inhibition, and the activation parameters, a mechanism involving dissociative CO loss as the rate-limiting step is proposed. The solid-state structure of CoRu(CO)4(μ -bma)(μ -PPh2) (3) reveals that the two PPh2 groups are bound to the ruthenium center while the maleic anhydride π bond is coordinated to the cobalt atom. Thermolysis of the cluster Ru3(CO)12 with the bis(phosphine)hydrazine ligand (MeO)2PN(Me)N(Me)P(OMe)2 (dmpdmh) in toluene at 75°C furnishes the known clusters Ru4(CO)12[μ -N(Me)N(Me)] (9) and Ru3(CO)11[P(OMe)3] (10), in addition to the new cluster Ru3(CO)10(dmpdmh) (8) and the phosphite-tethered cluster Ru3(CO)9[μ -P(OMe)3] (11). The simple substitution product Ru3(CO)10(dmpdmh), a logical intermediate to clusters 9-11, was synthesized by treating Ru3(CO)12 and dmpdmh with Me3NO in CH2Cl2 at room temperature, and independent thermolysis reactions using cluster 8 were shown to yield clusters 9-11. The tetrahedrane cluster FeCo2(CO)9(μ3-S) reacts with the redox-active ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) to give the disubstituted cluster FeCo2(CO)7(bpcd)(μ3-S) as the sole product. This diphosphine-substituted cluster contains a cobalt-bound, chelating bpcd ligand. The solid-state structure has been unequivocally established by X-ray diffraction analysis. Cyclic voltammetric studies on FeCo2(CO)7(bpcd)(μ3-S) reveal the presence of two quasireversible redox responses assigned to the 0/1- and 1-/2- redox couples. The orbital composition of these redox couples has been examined by carrying out extended Hückel MO calculations on the model complex FeCo2(CO)7(H4-bpcd)(μ3-S), with the results being compared to related cluster compounds."]},{"key":"dc:format","label":"Dc Format","values":["Text"]},{"key":"dc:title","label":"Title","values":["Diphosphine Ligand Activation Studies with Organotransition-Metal Compounds"]}]}],"canonical_facts":{"dc:contributor":["Richmond, Michael","Schwartz, Martin","Golden, Teresa D.","Wiedenfeld, David"],"dc:creator":["Wang, Jiancheng"],"dc:date":["2000-12"],"dc:description":["Thermolysis of CoRu(CO)7(m -PPh2) (1) in refluxing 1,2-dichloroethane in the presence of the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the new mixed-metal complexes CoRu(CO)4(μ -P-P)(μ -PPh2) [where P-P = bma (3); bpcd (6)], along with trace amounts of the known complex CoRu(CO)6(PPh3)(μ -PPh2) (4). The requisite pentacarbonyl intermediates CoRu(CO)5(μ -P-P)(μ -PPh2) [where P-P = bma (2); bpcd (5)] have been prepared by separate routes and studied for their conversion to CoRu(CO)4(μ -P-P)(μ -PPh2). The complexes 2/3 and 5/6 have been isolated and fully characterized in solution by IR and NMR spectroscopy. The kinetics for the conversion of 2→3 and of 5→6 were measured by IR spectroscopy in chlorobenzene solvent. On the basis of the first-order rate constants, CO inhibition, and the activation parameters, a mechanism involving dissociative CO loss as the rate-limiting step is proposed. The solid-state structure of CoRu(CO)4(μ -bma)(μ -PPh2) (3) reveals that the two PPh2 groups are bound to the ruthenium center while the maleic anhydride π bond is coordinated to the cobalt atom. Thermolysis of the cluster Ru3(CO)12 with the bis(phosphine)hydrazine ligand (MeO)2PN(Me)N(Me)P(OMe)2 (dmpdmh) in toluene at 75°C furnishes the known clusters Ru4(CO)12[μ -N(Me)N(Me)] (9) and Ru3(CO)11[P(OMe)3] (10), in addition to the new cluster Ru3(CO)10(dmpdmh) (8) and the phosphite-tethered cluster Ru3(CO)9[μ -P(OMe)3] (11). The simple substitution product Ru3(CO)10(dmpdmh), a logical intermediate to clusters 9-11, was synthesized by treating Ru3(CO)12 and dmpdmh with Me3NO in CH2Cl2 at room temperature, and independent thermolysis reactions using cluster 8 were shown to yield clusters 9-11. The tetrahedrane cluster FeCo2(CO)9(μ3-S) reacts with the redox-active ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) to give the disubstituted cluster FeCo2(CO)7(bpcd)(μ3-S) as the sole product. This diphosphine-substituted cluster contains a cobalt-bound, chelating bpcd ligand. The solid-state structure has been unequivocally established by X-ray diffraction analysis. Cyclic voltammetric studies on FeCo2(CO)7(bpcd)(μ3-S) reveal the presence of two quasireversible redox responses assigned to the 0/1- and 1-/2- redox couples. The orbital composition of these redox couples has been examined by carrying out extended Hückel MO calculations on the model complex FeCo2(CO)7(H4-bpcd)(μ3-S), with the results being compared to related cluster compounds."],"dc:format":["Text"],"dc:identifier":["oclc: 47785437","doi: 10.12794/metadc2665","https://digital.library.unt.edu/ark:/67531/metadc2665/","ark: ark:/67531/metadc2665"],"dc:language":["English"],"dc:publisher":["University of North Texas"],"dc:rights":["Use restricted to UNT Community","Copyright","Wang, Jiancheng","Copyright is held by the author, unless otherwise noted. All rights reserved."],"dc:subject":["Ligands.","Organotransition metal compounds.","CoRu(CO)4(μ -P-P)(μ -PPh2)","Ru3(CO)10(dmpdmh)","thermolysis","diphosphine ligands","new mixed-metalcomplexes"],"dc:title":["Diphosphine Ligand Activation Studies with Organotransition-Metal Compounds"],"dc:type":["Thesis or Dissertation"]},"updated_at":"2026-07-24T05:34:52Z"}