{"id":{"repo_id":"buffalo","oai_identifier":"oai:ubir.buffalo.edu:10477/86675"},"canonical_url":"https://search.dev.ndltd.org/etd/buffalo/oai:ubir.buffalo.edu:10477/86675","repository":{"repo_id":"buffalo","name":"Buffalo","base_url":"https://ubir.buffalo.edu/oai/request"},"display":{"title":"Synthesis, Reactivity, and Thermochemistry of Mn(I) Carbonyl Complexes with Hydroxide and Phenol-Phosphine Ligands","abstract":"Ph.D.","abstract_html":"Ph.D.","abstract_has_math":false,"creators":["Kadassery, Karthika Jairaj; 0000-0003-2065-1356"],"institution":"State University of New York at Buffalo","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Lacy, David","Chemistry"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2025,"date_issued":"2025-02-21T21:36:20Z","date_published":"2025-02-21T21:36:20Z","updated_at":"2026-07-27T19:05:34Z","subjects":["chemistry","inorganic chemistry"],"languages":["eng"],"rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10477/86675","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Lacy, David","Chemistry"]},{"key":"dc:creator","label":"Author","values":["Kadassery, Karthika Jairaj; 0000-0003-2065-1356"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2025-02-21T21:36:20Z","2020"]},{"key":"dc:publisher","label":"Institution","values":["State University of New York at Buffalo"]},{"key":"dc:type","label":"Dc Type","values":["Text","Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["chemistry","inorganic chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/10477/86675"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Ph.D.","Manganese is a first-row transition metal, predominantly found in the Earth's crust where it is the third-most abundant transition metal after iron and titanium. In Industry, manganese is produced on a massive scale and is extensively used in the preparation of metal alloys, catalysts in radical chain aerobic oxidations, and antiknock fuel additives. Manganese also plays an important role in biology as an essential micronutrient that is necessary for the proper functioning of the human body. In plants, manganese is involved in photosynthesis and is a critical component of the oxygen-evolving complex, a tetranuclear Mn4CaO5 center that oxidizes water to O2. Despite being a versatile metal with applications spanning across biology and industry, the chemistry of Mn has lagged behind other transition metals (e.g. iron and copper). However, the 2016 discovery of Mn(I) catalyzed (de)hydrogenations by Milstein and Beller led to an explosion of investigations surrounding the chemistry of Mn(I) all across the globe. While these reports revealed the potential of manganese as a substitute for expensive and toxic metals in catalysis, previous reports from Fan and coworkers showed its potential in hydrogen production and energy science. For instance, they reported that an organomanganese complex, cymantrene (CpMn(CO)3), can photochemically split water to give H2 and H2O2 in stoichiometric amounts. It is interesting to note that the same group reported cymantrene catalyzed photochemical splitting of thiols (RSH) into H2 and disulfides (RS-SR).Inspired by these findings, we investigated the photochemical properties of a known tetrameric complex [Mn(CO)3(µ3-OH)]4 and demonstrated the production of H2 and H2O2 upon irradiation of the complex in a biphasic (water/toluene) mixture. Our studies with this complex revealed some mechanistic insights about the species resulting from disproportionation and disassembly of the cluster. Attempts to stabilize these intermediates for a deeper understanding of the water-splitting mechanism led us to strategically design and develop a phenolic POP pincer ligand platform. Unfortunately, the POP ligands failed at stabilizing the cluster and hence provided no additional insights into the water-splitting chemistry. However, these ligands gave rise to rich coordination chemistry with manganese owing to their hemilabile phenol(ate) group and yielded various mono and multi-nuclear complexes. Screening these complexes for application in catalyzing various organic transformations led to our discovery of the very first Mn(I) catalyzed Tishchenko reaction (conversion of aldehydes to esters). This discovery was a well-timed addition to the extensive list of catalysis carried out by various Mn(I) complexes, reported since the very recent discovery of Mn(I) catalyzed (de)hydrogenations via metal-ligand cooperativity (MLC) in 2016...","**To request an accessible version of the file(s) associated with this item, contact library@buffalo.edu. Please include the item's persistent URL [http://hdl.handle.net/. . .] in your request.**"]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Synthesis, Reactivity, and Thermochemistry of Mn(I) Carbonyl Complexes with Hydroxide and Phenol-Phosphine Ligands"]}]}],"canonical_facts":{"dc:contributor":["Lacy, David","Chemistry"],"dc:creator":["Kadassery, Karthika Jairaj; 0000-0003-2065-1356"],"dc:date":["2025-02-21T21:36:20Z","2020"],"dc:description":["Ph.D.","Manganese is a first-row transition metal, predominantly found in the Earth's crust where it is the third-most abundant transition metal after iron and titanium. In Industry, manganese is produced on a massive scale and is extensively used in the preparation of metal alloys, catalysts in radical chain aerobic oxidations, and antiknock fuel additives. Manganese also plays an important role in biology as an essential micronutrient that is necessary for the proper functioning of the human body. In plants, manganese is involved in photosynthesis and is a critical component of the oxygen-evolving complex, a tetranuclear Mn4CaO5 center that oxidizes water to O2. Despite being a versatile metal with applications spanning across biology and industry, the chemistry of Mn has lagged behind other transition metals (e.g. iron and copper). However, the 2016 discovery of Mn(I) catalyzed (de)hydrogenations by Milstein and Beller led to an explosion of investigations surrounding the chemistry of Mn(I) all across the globe. While these reports revealed the potential of manganese as a substitute for expensive and toxic metals in catalysis, previous reports from Fan and coworkers showed its potential in hydrogen production and energy science. For instance, they reported that an organomanganese complex, cymantrene (CpMn(CO)3), can photochemically split water to give H2 and H2O2 in stoichiometric amounts. It is interesting to note that the same group reported cymantrene catalyzed photochemical splitting of thiols (RSH) into H2 and disulfides (RS-SR).Inspired by these findings, we investigated the photochemical properties of a known tetrameric complex [Mn(CO)3(µ3-OH)]4 and demonstrated the production of H2 and H2O2 upon irradiation of the complex in a biphasic (water/toluene) mixture. Our studies with this complex revealed some mechanistic insights about the species resulting from disproportionation and disassembly of the cluster. Attempts to stabilize these intermediates for a deeper understanding of the water-splitting mechanism led us to strategically design and develop a phenolic POP pincer ligand platform. Unfortunately, the POP ligands failed at stabilizing the cluster and hence provided no additional insights into the water-splitting chemistry. However, these ligands gave rise to rich coordination chemistry with manganese owing to their hemilabile phenol(ate) group and yielded various mono and multi-nuclear complexes. Screening these complexes for application in catalyzing various organic transformations led to our discovery of the very first Mn(I) catalyzed Tishchenko reaction (conversion of aldehydes to esters). This discovery was a well-timed addition to the extensive list of catalysis carried out by various Mn(I) complexes, reported since the very recent discovery of Mn(I) catalyzed (de)hydrogenations via metal-ligand cooperativity (MLC) in 2016...","**To request an accessible version of the file(s) associated with this item, contact library@buffalo.edu. Please include the item's persistent URL [http://hdl.handle.net/. . .] in your request.**"],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/10477/86675"],"dc:language":["eng"],"dc:publisher":["State University of New York at Buffalo"],"dc:rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"dc:subject":["chemistry","inorganic chemistry"],"dc:title":["Synthesis, Reactivity, and Thermochemistry of Mn(I) Carbonyl Complexes with Hydroxide and Phenol-Phosphine Ligands"],"dc:type":["Text","Dissertation"]},"updated_at":"2026-07-27T19:05:34Z"}