Date of Award
9-6-2024
Degree Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
First Advisor
Dali Liu
Abstract
A solvent free synthesis of chloro-bridge dimers [LFe(μ-Cl)]2 and [LCo(μ-Cl)]2 supported by an asymmetric N-alkyl,N′-aryl-β-diketiminate ligand L (L = 2-((S)-(-)-1-phenylethylimino)-4-(2,6-diisopropylphenylimido)pentane) is presented. Rare examples of low-valent complexes LFe(cod) and LCo(cod) can be obtained by reducing the chloro-bridged dimers in the presence of cis-cyclooctadiene. The metal complexes have been successfully characterized by 1H NMR spectroscopy, elemental analysis, and X-ray crystallography. As supported by Crystallographic and spectroscopic results, the N-alkyl,N′-aryl-β-diketiminate ligand L is sterically smaller yet a better electron donor than the N,N′-diaryl-substituted β-diketiminate ligand LMe,Dipp (LMe,Dipp = 2,4-bis(2,6-diisopropylphenylimido)pentane). The N-alkyl, N′-aryl-β-diketiminate ligand L was used to support the bimetallic assembly of [2Fe–2E] (E = S and Se). The Sulfur analog displays an unusually long Fe⋯Fe distance, but that of the Selenium analog is comparable to reported Fe…Fe distances in the literature. As evident by electronic spectroscopy and electrochemical analysis, these two model complexes possess varying electron transfer capabilities. The formation mechanism of the compound is suggested by the kinetic data and activation parameters. Additionally, atom transfer reactivity has been investigated to probe the possible sulfur-transfer mechanism of [2Fe–2S] clusters.
Recommended Citation
Weerawardhana, Erwin Anuruddhika, "[2Fe–2E] Model Compounds: Synthesis, Kinetic Studies, And Atom Transfer Reactivity" (2024). Dissertations. 4100.
https://ecommons.luc.edu/luc_diss/4100
