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Thiolate, Phosphide, and Hydride Iron-Carbide Clusters to Model FeMoco: Leveraging Polyhedral Skeletal Electron Pair Theory (PSEPT) for Controlled Ligand Substitution on Iron Carbide Carbonyl Clusters
Thiolate, Phosphide, and Hydride Iron-Carbide Clusters to Model FeMoco: Leveraging Polyhedral Skeletal Electron Pair Theory (PSEPT) for Controlled Ligand Substitution on Iron Carbide Carbonyl Clusters
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260311091502.5
- ISBN
- 9798270235154
- DDC
- 546
- 저자명
- Cobb, Caitlyn R.
- 서명/저자
- Thiolate, Phosphide, and Hydride Iron-Carbide Clusters to Model FeMoco: Leveraging Polyhedral Skeletal Electron Pair Theory (PSEPT) for Controlled Ligand Substitution on Iron Carbide Carbonyl Clusters / Caitlyn R Cobb
- 발행사항
- [Sl] : The University of Texas at Austin, 2025
- 형태사항
- 1 electronic resource (325 pages)
- 주기사항
- Source: Dissertations Abstracts International, Volume: 87-06, Section: B.
- 주기사항
- Advisors: Rose, Michael J. Committee members: Berben, Louise A.; Humphrey, Simon M.; Lu, Yi.
- 학위논문주기
- - Ph.D. : The University of Texas at Austin, 2025.
- 초록/해제
- 요약The structural modeling of the active site of nitrogenase (FeMoco) is a prevailing goal for synthetic bioinorganic chemists due to the importance of nitrogenases' nitrogen fixation ability and the unusual structure of the FeMoco cofactor among other iron sulfur clusters in biology due to its interstitial carbide. The goal of this body of work is to synthesize novel iron carbide carbonyl clusters with biologically relevant ligands and iron oxidation states. The synthetic challenge is how to convert a strong-field cluster with an octahedral Fe6-C core into a weak field cluster without decomposition of the carbide moiety. Herein, we report synthetically tractable methods for controlled substitutions of carbonyls with electron donating and anionic ligands onto iron carbide carbonyl clusters. First, we show that using sulfenyl chlorides as neutral oxidants and thiolate sources allows for one-pot insertion of thiolates onto iron carbide carbonyl clusters. We also demonstrate that stable neutral clusters are substitutionally active with thiolates. We then take these lessons and Polyhedral Skeletal Electron Pair Theory (PSEPT) to develop an in situ oxidation approach to screen various mono and multi-dentate phosphines and thiolate ligand reactions. We report the resultant insights into cluster decomposition and ligand design principles for stable multi-iron chelation of an iron-carbide core, notably including the first structurally characterized multi-iron chelated iron carbide carbonyl cluster. Next, we extend our manipulation of PSEPT to generate an anionic electron-starved intermediate that is substitutionally active due to PSEPT, but resistant to reduction by anionic ligands and to iron loss upon substitution due to its negative charge. Finally, we apply these synthetic methods to the insertion of phosphide ligands and report the structural characterization of five- and six-iron multi-phosphide and phosphide-hydride clusters with increased average iron oxidation states. Multi-hydride derivatives of these structurally characterized clusters are spectroscopically characterized. The combined synthetic methods and insights herein should serve as a toolkit for the development of novel, tunable synthetic models of FeMoco capable of stabilizing both increased iron oxidation states and biologically relevant hydrides, moving from structural models of the resting state toward the goal of structure-function modeling.
- 언어주기
- English
- 일반주제명
- Analytical chemistry
- 일반주제명
- Organic chemistry
- 키워드
- Nitrogenase
- 키워드
- Carbonyls
- 키워드
- Thiolates
- 기타저자
- The University of Texas at Austin Chemistry
- 기본자료저록
- Dissertations Abstracts International. 87-06B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
008260311s2025 us eng d■001000017361272
■00520260311091502.5
■006m o d
■007cr|nu||||||||
■020 ▼a9798270235154
■040 ▼aMiAaPQD▼beng▼cMiAaPQD▼erda
■082 ▼a546
■1001 ▼aCobb, Caitlyn R.▼eauthor.
■24510▼aThiolate, Phosphide, and Hydride Iron-Carbide Clusters to Model FeMoco: Leveraging Polyhedral Skeletal Electron Pair Theory (PSEPT) for Controlled Ligand Substitution on Iron Carbide Carbonyl Clusters ▼cCaitlyn R Cobb
■260 ▼a[Sl]▼bThe University of Texas at Austin▼c2025
■264 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2025
■300 ▼a1 electronic resource (325 pages)
■336 ▼atext▼btxt▼2rdacontent
■337 ▼acomputer▼bc▼2rdamedia
■338 ▼aonline resource▼bcr▼2rdacarrier
■500 ▼aSource: Dissertations Abstracts International, Volume: 87-06, Section: B.
■500 ▼aAdvisors: Rose, Michael J. Committee members: Berben, Louise A.; Humphrey, Simon M.; Lu, Yi.
■5021 ▼bPh.D.▼cThe University of Texas at Austin▼d2025.
■520 ▼aThe structural modeling of the active site of nitrogenase (FeMoco) is a prevailing goal for synthetic bioinorganic chemists due to the importance of nitrogenases' nitrogen fixation ability and the unusual structure of the FeMoco cofactor among other iron sulfur clusters in biology due to its interstitial carbide. The goal of this body of work is to synthesize novel iron carbide carbonyl clusters with biologically relevant ligands and iron oxidation states. The synthetic challenge is how to convert a strong-field cluster with an octahedral Fe6-C core into a weak field cluster without decomposition of the carbide moiety. Herein, we report synthetically tractable methods for controlled substitutions of carbonyls with electron donating and anionic ligands onto iron carbide carbonyl clusters. First, we show that using sulfenyl chlorides as neutral oxidants and thiolate sources allows for one-pot insertion of thiolates onto iron carbide carbonyl clusters. We also demonstrate that stable neutral clusters are substitutionally active with thiolates. We then take these lessons and Polyhedral Skeletal Electron Pair Theory (PSEPT) to develop an in situ oxidation approach to screen various mono and multi-dentate phosphines and thiolate ligand reactions. We report the resultant insights into cluster decomposition and ligand design principles for stable multi-iron chelation of an iron-carbide core, notably including the first structurally characterized multi-iron chelated iron carbide carbonyl cluster. Next, we extend our manipulation of PSEPT to generate an anionic electron-starved intermediate that is substitutionally active due to PSEPT, but resistant to reduction by anionic ligands and to iron loss upon substitution due to its negative charge. Finally, we apply these synthetic methods to the insertion of phosphide ligands and report the structural characterization of five- and six-iron multi-phosphide and phosphide-hydride clusters with increased average iron oxidation states. Multi-hydride derivatives of these structurally characterized clusters are spectroscopically characterized. The combined synthetic methods and insights herein should serve as a toolkit for the development of novel, tunable synthetic models of FeMoco capable of stabilizing both increased iron oxidation states and biologically relevant hydrides, moving from structural models of the resting state toward the goal of structure-function modeling.
■546 ▼aEnglish
■590 ▼aSchool code: 0227
■650 4▼aAnalytical chemistry
■650 4▼aOrganic chemistry
■653 ▼aNitrogenase
■653 ▼aCarbonyls
■653 ▼aThiolates
■653 ▼aIron oxidation states
■7102 ▼aThe University of Texas at Austin▼bChemistry.▼edegree granting institution.
■7201 ▼aRose, Michael J.▼edegree supervisor.
■7730 ▼tDissertations Abstracts International▼g87-06B.
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17361272▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
