Digitized Honors Theses (2002-2017)

Date of Award

5-2006

Document Type

Undergraduate Thesis

Degree Name

BS

Department

Chemistry

Faculty Mentor

Norris Hoffman

Abstract

A set of divalent nickel-triad fluorinated-pincer complexes containing diorganophosphinite pendant arms has been synthesized to (i) compare structure and reactivity for the phenyl (Ph) and isopropyl (Pri) palladium(II) versions and for the isopropyl (P;) 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 n3-4-F-C3H2-2,6-(OPR2)2-M-X have been measured by 19F NMR (and corroborated by 31P) in CDCl3 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 [n3-4-F-C6H2-2,6-(OPR2)2-M-L]+. Relative affinities for L of varying stereoelectronic natures have also been determined by 19F and 31P NMR in CDCl3 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.

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