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Probing the Reactivity of Uncommon Palladium Oxidation States
Probing the Reactivity of Uncommon Palladium Oxidation States
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202105655
- ISBN
- 9798265452412
- DDC
- 546
- 서명/저자
- Probing the Reactivity of Uncommon Palladium Oxidation States
- 발행사항
- [Sl] : University of Illinois at Urbana-Champaign, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 332 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 87-06, Section: B.
- 주기사항
- Advisor: Mirica, Liviu M.
- 학위논문주기
- Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2024.
- 초록/해제
- 요약The chemistry of palladium (Pd) has been extensively interrogated in the last few decades, especially in the realm of bond forming reactions. Carbon-carbon (C-C) cross-coupling reactions are one of the most prevalent modern pharmaceutical transformations, and are commonly mediated by homogeneous Pd-based catalysts. Traditionally, most Pd cross coupling perform under a unified catalytic cycle, operating in even oxidation states (0/II) with remarkable predictability and stability. However, as we expand our repertoire of reactivity, the so-called "odd" oxidation states have garnered additional academic scrutiny, especially in photochemical and radical-based processes. Accessing this chemistry with intention has potential benefits, as (I/III) cycles could result in lower rates of β-hydride elimination due to poorer d-orbital overlap with alkyl ligands, allowing the use of sp3 reactants, and radical oxidative addition processes could allow for the use of electrophiles that cannot be easily activated with classical Pd catalysts. Despite these potential benefits, the unstable nature of Pd(I) and Pd(III) complexes makes characterization of these ions difficult, and our understanding of how odd oxidation state Pd complexes react is limited. Our group has shown that pyridinophane macrocycles can be used to stabilize these oxidation states to probe their reactivity by creating a distorted octahedral geometry around the metal ion. This strategy has been expanded upon in this document to explore not only the high, but also the low-valent chemistry in the areas of Pd(I/III) catalytic transformations and C-H activation. These results help to better frame the general reactivity principles of these uncommon palladium oxidation states.
- 일반주제명
- Inorganic chemistry
- 일반주제명
- Chemistry
- 키워드
- Cross-coupling
- 키워드
- Mechanism
- 기타저자
- University of Illinois at Urbana-Champaign Chemistry
- 기본자료저록
- Dissertations Abstracts International. 87-06B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■020 ▼a9798265452412
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■035 ▼a(MiAaPQ)124662
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a546
■1001 ▼aBouley, Bailey Samuel.
■24510▼aProbing the Reactivity of Uncommon Palladium Oxidation States
■260 ▼a[Sl]▼bUniversity of Illinois at Urbana-Champaign▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a332 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 87-06, Section: B.
■500 ▼aAdvisor: Mirica, Liviu M.
■5021 ▼aThesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2024.
■520 ▼aThe chemistry of palladium (Pd) has been extensively interrogated in the last few decades, especially in the realm of bond forming reactions. Carbon-carbon (C-C) cross-coupling reactions are one of the most prevalent modern pharmaceutical transformations, and are commonly mediated by homogeneous Pd-based catalysts. Traditionally, most Pd cross coupling perform under a unified catalytic cycle, operating in even oxidation states (0/II) with remarkable predictability and stability. However, as we expand our repertoire of reactivity, the so-called "odd" oxidation states have garnered additional academic scrutiny, especially in photochemical and radical-based processes. Accessing this chemistry with intention has potential benefits, as (I/III) cycles could result in lower rates of β-hydride elimination due to poorer d-orbital overlap with alkyl ligands, allowing the use of sp3 reactants, and radical oxidative addition processes could allow for the use of electrophiles that cannot be easily activated with classical Pd catalysts. Despite these potential benefits, the unstable nature of Pd(I) and Pd(III) complexes makes characterization of these ions difficult, and our understanding of how odd oxidation state Pd complexes react is limited. Our group has shown that pyridinophane macrocycles can be used to stabilize these oxidation states to probe their reactivity by creating a distorted octahedral geometry around the metal ion. This strategy has been expanded upon in this document to explore not only the high, but also the low-valent chemistry in the areas of Pd(I/III) catalytic transformations and C-H activation. These results help to better frame the general reactivity principles of these uncommon palladium oxidation states.
■590 ▼aSchool code: 0090.
■650 4▼aInorganic chemistry
■650 4▼aChemistry
■653 ▼aPalladium oxidation states
■653 ▼aCross-coupling
■653 ▼aOrganometallic ligands
■653 ▼aMechanism
■690 ▼a0488
■690 ▼a0485
■71020▼aUniversity of Illinois at Urbana-Champaign▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g87-06B.
■790 ▼a0090
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17361035▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
