Date of Award
5-2018
Degree Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
Committee Chair
Christopher Uyeda
Committee Member 1
Mingji Dai
Committee Member 2
Corey Thompson
Committee Member 3
Jianguo Mei
Abstract
Strained, three-membered rings were found to undergo oxidative addition to [iPrNDI]Ni2(C6H6) complex [NDI = napthyridine-diimine). Activation of the C-N bond of 1-tosyl-2-vinylaziridine generates a dinickel metallacyclic product. Based on this reactivity, the [iPrNDI]Ni2(C6H6) complex was shown to be a highly active catalyst for rearranging vinylcyclopropanes to cyclopentenes. Notably, 2-phenyl-1-vinylcyclopropane undergoes regioselective activation at the less hindered C–C bond in contrast to the non-catalytic thermal rearrangement. The dinuclear complex was also found to readily rearrange hetero-atom containing cyclopropanes to their linear products. DFT calculations provide insight into the ability of the Ni–Ni bond to stabilize key intermediates and transition states along the catalytic pathway. Hetero-atom abstraction was also observed in the activation of other strained, three-membered rings with the [iPrNDI]Ni2(C6H6) complex. Crystal structures were obtained from the activation of sulfur containing heterocycles and their characteristics are currently being investigated to design catalytic desulfurization reactions.
Recommended Citation
Rounds, Heather, "Oxidative Transfer Reactions at a Metal-Metal Bond" (2018). Open Access Dissertations. 1812.
https://docs.lib.purdue.edu/open_access_dissertations/1812