Digitized Honors Theses (2002-2017)

Date of Award

5-2006

Document Type

Undergraduate Thesis

Degree Name

BS

Department

Chemistry

Faculty Mentor

Norris Hoffman, Ph.D.

Advisor(s)

Richard Sykora, Ph.D., Eugene Cioffi, Ph.D.

Abstract

A set of divalent nickel-triad fluorinated-pincer complexes containing diorganophosphinite pendant anns has been synthesized to (i) compare structure and reactivity for the phenyl (Ph) and isopropyl (Pri) palladium(Il) versions and for the isopropyl (Pt) palladium(II) and nickel(Il) forms, and (ii) to demonstrate the utility of the 19F NMR- reporter function in equilibrium studies. Relative anion affinities in 113-4-F-CJii-2,6-(0PR 2)2-M-X have been measured by 19F NMR (and corroborated by 31P) in CDC1 for the halides, nitrate, trifluoroacetate, and three artificial sweetener anions using N(PPh3)2+ salts. Halide abstraction from the neutral species using Tl(I) in the presence of neutral ligands has afforded a large set of cations [113-4-F-C6H2-2,6-(0PR2)2-M-Lt. Relative affinities for L of varying stereoelectronic natures have also been determined by 19F and 31P NMR in CDCh to determine how the identity of bis-phosphinite R affects the cationic metal center. Many of these cationic species have been studied by ESI-ICR-Infrared Multiphoton Dissociation to correlate their activation energies for gas-phase loss of neutral L with thermodynamic solution-phase affinity of the metal center for L. Crystal structures of several complexes studied have been obtained.

Comments

© 2006 Rachel Kristina Traylor ALL RIGHTS RESERVED

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