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Unusual Admissions of Guilt: Novel Redox Non-Innocent Chelates for Base Metal Chemistry and a Comparative Study on the Charge-Reporting Ability of Nitrosyl Ligands
Unusual Admissions of Guilt: Novel Redox Non-Innocent Chelates for Base Metal Chemistry and a Comparative Study on the Charge-Reporting Ability of Nitrosyl Ligands
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211151151
- ISBN
- 9798382840376
- DDC
- 546
- 서명/저자
- Unusual Admissions of Guilt: Novel Redox Non-Innocent Chelates for Base Metal Chemistry and a Comparative Study on the Charge-Reporting Ability of Nitrosyl Ligands
- 발행사항
- [Sl] : Cornell University, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 170 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 85-12, Section: B.
- 주기사항
- Includes supplementary digital materials.
- 주기사항
- Advisor: Wolczanski, Peter.
- 학위논문주기
- Thesis (Ph.D.)--Cornell University, 2024.
- 초록/해제
- 요약Redox non-innocence (RNI) allows organometallic chemists to impart greater covalency to first row transition metals (TMs) to replicate the reactivity of noble metal congeners. A new, non-innocent tetradentate β-diimine chelate (pddiH2) has been synthesized and coordinated to Cr, Fe, and Co. Treatment of pddiCr with several reagents revealed that cyclopropanation in the ligand backbone could reversibly occur, and several forays into reactivity were conducted. Some exploration into using simple β-diimines as RNI chelates was also performed, generating several new complexes with minimal activity. Another classic example of a redox non-innocent ligand is the nitrosyl. Their electronic ambiguity is well documented, with three redox states available-NO+, NO•, and NO-. The uncertainty in assignment combined with the ligand's spectroscopic handle, ν(NO), allowed for extension of the previously developed system of charge distribution via reporters (CDVR) to M-NO species. First row TM complexes from the Cambridge Structural Database were examined to look for correlations between the calculated charge, cNO, and several metrics, namely d(N-O) and ∠M-N-O. This comparative study allowed for the development of a phenomenological equation of charge for LnM-NO. Several novel mononitrosyl complexes that displayed puzzling and contradictory experimental metrics (e.g. XRD and IR analyses) were also analyzed.
- 일반주제명
- Inorganic chemistry
- 일반주제명
- Chemistry
- 일반주제명
- Materials science
- 기타저자
- Cornell University Chemistry and Chemical Biology
- 기본자료저록
- Dissertations Abstracts International. 85-12B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■020 ▼a9798382840376
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■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a546
■1001 ▼aD'Arpino, Alexander Angelo.▼0(orcid)0000-0003-0991-096X
■24510▼aUnusual Admissions of Guilt: Novel Redox Non-Innocent Chelates for Base Metal Chemistry and a Comparative Study on the Charge-Reporting Ability of Nitrosyl Ligands
■260 ▼a[Sl]▼bCornell University▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a170 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 85-12, Section: B.
■500 ▼aIncludes supplementary digital materials.
■500 ▼aAdvisor: Wolczanski, Peter.
■5021 ▼aThesis (Ph.D.)--Cornell University, 2024.
■520 ▼aRedox non-innocence (RNI) allows organometallic chemists to impart greater covalency to first row transition metals (TMs) to replicate the reactivity of noble metal congeners. A new, non-innocent tetradentate β-diimine chelate (pddiH2) has been synthesized and coordinated to Cr, Fe, and Co. Treatment of pddiCr with several reagents revealed that cyclopropanation in the ligand backbone could reversibly occur, and several forays into reactivity were conducted. Some exploration into using simple β-diimines as RNI chelates was also performed, generating several new complexes with minimal activity. Another classic example of a redox non-innocent ligand is the nitrosyl. Their electronic ambiguity is well documented, with three redox states available-NO+, NO•, and NO-. The uncertainty in assignment combined with the ligand's spectroscopic handle, ν(NO), allowed for extension of the previously developed system of charge distribution via reporters (CDVR) to M-NO species. First row TM complexes from the Cambridge Structural Database were examined to look for correlations between the calculated charge, cNO, and several metrics, namely d(N-O) and ∠M-N-O. This comparative study allowed for the development of a phenomenological equation of charge for LnM-NO. Several novel mononitrosyl complexes that displayed puzzling and contradictory experimental metrics (e.g. XRD and IR analyses) were also analyzed.
■590 ▼aSchool code: 0058.
■650 4▼aInorganic chemistry
■650 4▼aChemistry
■650 4▼aMaterials science
■653 ▼aBase metal chemistry
■653 ▼aMetal nitrosyl compound
■653 ▼aRedox non-innocence
■653 ▼aTransition metals
■690 ▼a0488
■690 ▼a0485
■690 ▼a0794
■71020▼aCornell University▼bChemistry and Chemical Biology.
■7730 ▼tDissertations Abstracts International▼g85-12B.
■790 ▼a0058
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17161023▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
