Abstract

This thesis is comprised of two key themes: (i) leveraging mechanochemical synthetic methods for the green preparation of bis(imino)pyridine ligands and associated first row transition metal coordination complexes, and (ii) the preparation and characterization of both historic and novel mid-valent inorganic synthons via the use of dimethylphenylsilane as a stoichiometric reducing agent. The first portion of this thesis highlights the utilization of solvent-free vibratory ball-milling in lieu of traditional, solvent-based refluxes. A variety of both bis(imino)pyridine ligands and complexes were formed in drastically reduced timeframes with solvent-economical work-up procedures. This methodology was also leveraged for the isolation of acetyl(imino)pyridine ligands which, in turn, provided direct access to an unsymmetrical bis(imino)pyridine ligand in good yield. The second portion of this thesis is centered on the preparation of ether-coordinated, mid-valent, early transition metal chloride precursors. First, well-established, reproducible syntheses and characterization libraries were developed for the classic molybdenum(IV) and tungsten(IV) chloride diethyl ether- and dimethoyxethane-coordinated synthons. Then, the utilization of commercially available dimethylphenylsilane as a stoichiometric reducing agent provided direct access to single crystals of the classic edge-sharing bioctahedral dimer Mo2Cl6(dme)2, whose single crystal x-ray structure and electronic structure had remained ambiguous for nearly 40 years. This work laid the foundation for the preparation of intriguingly reactive, uncoordinated, mid-valent binary chlorides of the heavier Group 5 and Group 6 transition metals. Utilization of the acquired binary chlorides resulted in both less expensive, easier routes to traditional synthons and the formation of novel, ether-coordinated complexes of niobium and tantalum. Synthesis, characterization, and computational studies are presented and discussed.

Notes

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Graduation Date

2022

Semester

Fall

Advisor

Jurca, Titel

Degree

Doctor of Philosophy (Ph.D.)

College

College of Sciences

Department

Chemistry

Degree Program

Chemistry

Identifier

CFE0009839; DP0027780

URL

https://purls.library.ucf.edu/go/DP0027780

Language

English

Release Date

June 2024

Length of Campus-only Access

1 year

Access Status

Doctoral Dissertation (Campus-only Access)

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