Date Approved

2007

Degree Type

Open Access Thesis

Degree Name

Master of Science (MS)

Department

Chemistry

Committee Member

Vance Kennedy, PhD, Chair

Committee Member

Timothy Brewer, PhD

Committee Member

Harriet Lindsay, PhD

Abstract

Part 1. The kinetics of the ligand exchange reaction between 5-methyl-1,10-phenanthroline and triethylenetetramine nickel (II) were studied spectrophotometrically over the pH range of 5.2 to 8.0 at 25oC. A ternary complex Ni(Trien)(5MP) forms within a few seconds and subsequently reacts with 5MP to form Ni(5MP)3. The reaction is first-order with respect to: [5MP], [Ni(Trien)(5MP)] and [H+]. The rate law is given by:

k dt d[Ni(trien)] = ( − MP Ni(trien)(5MP) + kH, 5MP Ni(trien)(5MP) [H+]) [Ni(trien)][5mp]

where: 5MP is 5-methyl-1,10-phenanthroline and k is the first order rate constant that has units of 1/time.

kH, 5mp Ni(trien)(5mp) = 9.78 X 104 M-2 s-1

and k5mp Ni(trien)(5mp) = 9.42 X 10-3 M-2 s-1

Part 2. Axial substitution on boron (III) subphthalocyanines (SubPcs) were investigated. The Boron subphthalocyanines BsubPcCl and BsubPcOH were synthesized. These derivatives were then used to prepare BsubPcSiHx3, BsubPcBu, and BsubPcOSi(CH2CH2CH2CH3)3. This study represents the first synthesis of axial substitution on boron subphthalocyanine with a tributylsiloxy group. The products were characterized by infrared spectroscopy, 1H nuclear magnetic resonance analysis, and high resolution mass spectroscopy.

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