{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/113260"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/113260","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis, characterization, and reactivity of high and low valent group 10 metal complexes supported by pyridine dithiolate ligands","abstract":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-08-01","abstract_html":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-08-01","abstract_has_math":false,"creators":["Tran, Giang Ngoc Huong"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Mirica, Liviu M.","Suslick, Kenneth S.","Fout, Allison R.","Olshansky, Lisa"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-01-12T22:51:41Z","date_published":"2022-01-12T22:51:41Z","updated_at":"2026-07-22T22:24:53Z","subjects":["Palladium","Pd(I) and Pd(II) complexes","mononuclear Pd(I)","catalysis","C–C bond formation","cross-coupling","C–H bond activation","organometallic Pd(III) complexes","nickel","electrocatalysis","hydrogen evolution reaction (HER)","Ni(I) complexes","organometallic Ni complexes","hydrogenase","bioinspired catalysts"],"languages":["en"],"rights":["Copyright 2021 Giang Tran"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/113260","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Mirica, Liviu M.","Suslick, Kenneth S.","Fout, Allison R.","Olshansky, Lisa"]},{"key":"dc:creator","label":"Author","values":["Tran, Giang Ngoc Huong"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-01-12T22:51:41Z","2024-01-12T22:56:20Z","2021-06-29","2021-08"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"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":["Palladium","Pd(I) and Pd(II) complexes","mononuclear Pd(I)","catalysis","C–C bond formation","cross-coupling","C–H bond activation","organometallic Pd(III) complexes","nickel","electrocatalysis","hydrogen evolution reaction (HER)","Ni(I) complexes","organometallic Ni complexes","hydrogenase","bioinspired catalysts"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2021 Giang Tran"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/113260"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-08-01","The student, Giang Tran, accepted the attached license on 2021-06-24 at 22:43.","The student, Giang Tran, submitted this Dissertation for approval on 2021-06-25 at 10:30.","This Dissertation was approved for publication on 2021-06-29 at 09:01.","Group 10 transition metals, especially palladium (Pd) and nickel (Ni), play an important role serving as catalysts for different transformations with a wide range of applications. However, beside the most commonly proposed M(0)/M(II) (M = Pd or Ni) catalytic cycles, there is still a limited understanding of the mechanisms that involve other less common key intermediates. Recent works have shown substantial evidence of the role of high valent M(III) and M(IV) species in catalytic organic transformations. Inspired by these new findings, our goal is to investigate the rarer oxidation states of these metal complexes to gain better insights into the different mechanisms. This study can potentially serve as a tool to design more efficient catalysts. Herein, we’ll discuss the +1 and +3 oxidation states of these metal centers, with a heavy focus on the low valent species. A series of dithiolate pyridinophane ligands were employed in these studies. With the presence of S atoms as the soft atom donor, we propose that these ligands can allow us to stabilize MI species based on the Hard Soft Acid Base theory. In our first study, we attempted to isolate Pd(I) intermediates with our multidentate ligands. To further enhance the stabilizing effect, we also incorporated ancillary ligands with soft P atoms. To our delight, two monomeric Pd(I) complexes – [(N2S2)Pd(I)(PtBu3)]+ and [(NCHS2)Pd(I)(PtBu3)]+ – were structurally characterized, and both of them showed superior catalytic reactivity for the Csp2-Csp3 Kumada cross-coupling reaction vs. their Pd(0) or Pd(II) analogs. These sulfur-based ligands were also employed to design different bioinspired Ni electrocatalysts for the study of electrochemical hydrogen evolution reaction (HER) in a non-aqueous electrolyte. These complexes are able to achieve stable catalytic currents with high turnover numbers for proton reduction, even at low acid concentration. Additionally, in contrast to the Ni(0)/Ni(II) process employed by most other reported Ni-based HER catalysts, one of our Ni species – [(NCHS2)NiOTf2 – is proposed to go through a Ni(I)/Ni(III) HER mechanism, which is similar to the natural process in [NiFe] hydrogenases. Extensive electrochemical experiments and EPR (Electron Paramagnetic Resonance) spectroscopic studies were carried out to provide evidence for the alternate Ni(I)/Ni(III) catalytic cycle. Lastly, preliminary results also showed that the multidentate pyridine dithiolate ligands can support organometallic Pd(III) species. Excitingly, the solid state structure of complex [(NCS2)Pd(III)(PPh3)]2+ was obtained, which showed a rare four-coordinate geometry at a Pd(III) center. Prior to this, no monomeric Pd(III) complex supported by S-based ligand(s) was structurally characterized. This is an important finding as it is uncommon for a ligand system to be able to stabilize both low and high valent metal species.","DSpace SAF Submission Ingestion Package generated from Vireo submission #16720 on 2022-01-12 at 13:03:41","Made available in DSpace on 2022-01-12T22:51:41Z (GMT). No. of bitstreams: 3 TRAN-DISSERTATION-2021.pdf: 8002319 bytes, checksum: 0343f705328bc5a736500dc7e0efbc8e (MD5) LICENSE.txt: 4207 bytes, checksum: 06849e03f41310c273439609703eabff (MD5) PROQUEST_LICENSE.txt: 4553 bytes, checksum: 34af2c6fc0b7d54cbc75dab47d43bda9 (MD5) Previous issue date: 2021-06-29","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:51:46Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:53:32Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:54:14Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:55:09Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:56:20Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Author requested closed access (OA after 2yrs) in Vireo ETD system","Limited"]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Synthesis, characterization, and reactivity of high and low valent group 10 metal complexes supported by pyridine dithiolate ligands"]}]}],"canonical_facts":{"dc:contributor":["Mirica, Liviu M.","Suslick, Kenneth S.","Fout, Allison R.","Olshansky, Lisa"],"dc:creator":["Tran, Giang Ngoc Huong"],"dc:date":["2022-01-12T22:51:41Z","2024-01-12T22:56:20Z","2021-06-29","2021-08"],"dc:description":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-08-01","The student, Giang Tran, accepted the attached license on 2021-06-24 at 22:43.","The student, Giang Tran, submitted this Dissertation for approval on 2021-06-25 at 10:30.","This Dissertation was approved for publication on 2021-06-29 at 09:01.","Group 10 transition metals, especially palladium (Pd) and nickel (Ni), play an important role serving as catalysts for different transformations with a wide range of applications. However, beside the most commonly proposed M(0)/M(II) (M = Pd or Ni) catalytic cycles, there is still a limited understanding of the mechanisms that involve other less common key intermediates. Recent works have shown substantial evidence of the role of high valent M(III) and M(IV) species in catalytic organic transformations. Inspired by these new findings, our goal is to investigate the rarer oxidation states of these metal complexes to gain better insights into the different mechanisms. This study can potentially serve as a tool to design more efficient catalysts. Herein, we’ll discuss the +1 and +3 oxidation states of these metal centers, with a heavy focus on the low valent species. A series of dithiolate pyridinophane ligands were employed in these studies. With the presence of S atoms as the soft atom donor, we propose that these ligands can allow us to stabilize MI species based on the Hard Soft Acid Base theory. In our first study, we attempted to isolate Pd(I) intermediates with our multidentate ligands. To further enhance the stabilizing effect, we also incorporated ancillary ligands with soft P atoms. To our delight, two monomeric Pd(I) complexes – [(N2S2)Pd(I)(PtBu3)]+ and [(NCHS2)Pd(I)(PtBu3)]+ – were structurally characterized, and both of them showed superior catalytic reactivity for the Csp2-Csp3 Kumada cross-coupling reaction vs. their Pd(0) or Pd(II) analogs. These sulfur-based ligands were also employed to design different bioinspired Ni electrocatalysts for the study of electrochemical hydrogen evolution reaction (HER) in a non-aqueous electrolyte. These complexes are able to achieve stable catalytic currents with high turnover numbers for proton reduction, even at low acid concentration. Additionally, in contrast to the Ni(0)/Ni(II) process employed by most other reported Ni-based HER catalysts, one of our Ni species – [(NCHS2)NiOTf2 – is proposed to go through a Ni(I)/Ni(III) HER mechanism, which is similar to the natural process in [NiFe] hydrogenases. Extensive electrochemical experiments and EPR (Electron Paramagnetic Resonance) spectroscopic studies were carried out to provide evidence for the alternate Ni(I)/Ni(III) catalytic cycle. Lastly, preliminary results also showed that the multidentate pyridine dithiolate ligands can support organometallic Pd(III) species. Excitingly, the solid state structure of complex [(NCS2)Pd(III)(PPh3)]2+ was obtained, which showed a rare four-coordinate geometry at a Pd(III) center. Prior to this, no monomeric Pd(III) complex supported by S-based ligand(s) was structurally characterized. This is an important finding as it is uncommon for a ligand system to be able to stabilize both low and high valent metal species.","DSpace SAF Submission Ingestion Package generated from Vireo submission #16720 on 2022-01-12 at 13:03:41","Made available in DSpace on 2022-01-12T22:51:41Z (GMT). No. of bitstreams: 3 TRAN-DISSERTATION-2021.pdf: 8002319 bytes, checksum: 0343f705328bc5a736500dc7e0efbc8e (MD5) LICENSE.txt: 4207 bytes, checksum: 06849e03f41310c273439609703eabff (MD5) PROQUEST_LICENSE.txt: 4553 bytes, checksum: 34af2c6fc0b7d54cbc75dab47d43bda9 (MD5) Previous issue date: 2021-06-29","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:51:46Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:53:32Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:54:14Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:55:09Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 121186 Lift date: 2024-01-12T22:56:20Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Author requested closed access (OA after 2yrs) in Vireo ETD system","Limited"],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/113260"],"dc:language":["en"],"dc:rights":["Copyright 2021 Giang Tran"],"dc:subject":["Palladium","Pd(I) and Pd(II) complexes","mononuclear Pd(I)","catalysis","C–C bond formation","cross-coupling","C–H bond activation","organometallic Pd(III) complexes","nickel","electrocatalysis","hydrogen evolution reaction (HER)","Ni(I) complexes","organometallic Ni complexes","hydrogenase","bioinspired catalysts"],"dc:title":["Synthesis, characterization, and reactivity of high and low valent group 10 metal complexes supported by pyridine dithiolate ligands"],"dc:type":["text","Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:24:53Z"}