자료유형  

 학위논문

Control Number  

0017161023

International Standard Book Number  

9798382840376

Dewey Decimal Classification Number  

546

Main Entry-Personal Name  

D'Arpino, Alexander Angelo.

Publication, Distribution, etc. (Imprint  

[S.l.] : Cornell University., 2024

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2024

Physical Description  

170 p.

General Note  

Source: Dissertations Abstracts International, Volume: 85-12, Section: B.

General Note  

Includes supplementary digital materials.

General Note  

Advisor: Wolczanski, Peter.

Dissertation Note  

Thesis (Ph.D.)--Cornell University, 2024.

Summary, Etc.  

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.

Subject Added Entry-Topical Term  

Inorganic chemistry.

Subject Added Entry-Topical Term  

Chemistry.

Subject Added Entry-Topical Term  

Materials science.

Index Term-Uncontrolled  

Base metal chemistry

Index Term-Uncontrolled  

Metal nitrosyl compound

Index Term-Uncontrolled  

Redox non-innocence

Index Term-Uncontrolled  

Transition metals

Added Entry-Corporate Name  

Cornell University Chemistry and Chemical Biology

Host Item Entry  

Dissertations Abstracts International. 85-12B.

Electronic Location and Access  

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Control Number  

joongbu:654709