Oxidative Addition Reactions at a Metal-Metal Bond

Heather Rounds, Purdue University

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.

Degree

Ph.D.

Advisors

Uyeda, Purdue University.

Subject Area

Organic chemistry

COinS