Physical Sciences and Mathematics Commons^™

Kinetics Of The Ligand Exchange Reactions Between Bidentate Ligands And Rriethylenetetramine Nickelate (Ii) And Synthesis Of Boron (Iii) Subphthalocyanines With Various Boron Substitutions, Michael Christopher Cate

Master's Theses and Doctoral Dissertations

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 …

An Investigation Into The Ring-Enlargement Reactions Of Boron Subphthalocyanine And Boron Subnaphthalocyanine, Andrew Jeremiah Jones

Master's Theses and Doctoral Dissertations

Ring enlargement syntheses of axially substituted boron subphthalocyanine and boron subnaphthalocyanine were investigated. The trihexylsiloxy derivatives of subphthalocyanine and subnaphthalocyanine were synthesized. These derivatives were then used in the ring-enlargement trials. Symmetrical and asymmetrical ring-enlargement reactions were carried out in a mixture of toluene and dimethylsulfoxide at room temperature. This study represents the first synthesis of boron subphthalocyanine with trihexylsiloxy group in the axial position and the first investigation into the ring enlargement of boron subnaphthalocyanine in which the axial ligand is a trihexylsiloxy group. Precipitates were formed, and it is believed that the precipitates are the metalfree ring-enlarged products. …