Doctor of Philosophy
Date of Defense
Eike Bauer, PhD
Several new η5-indenyl (Ind) complexes of iron featuring phosphinooxazoline (PHOX) ligands were synthesized and spectroscopically characterized and in a few cases structurally. The complexes were synthesized using phosphinooxazoline ligands and the corresponding iron precursor [Fe(η5-Ind) I(CO)2], yielding novel piano-stool iron complexes of the general formula [Fe(η5-Ind)(CO)(PHOX)]+ in 73% to 81% isolated yields. The complexes were tested for their efficacy in a carbon-carbon bond formation known as the Mukaiyama aldol reaction. The [Fe(η5-Ind)(CO)(PHOX)]+ complexes were capable of activating the carbonyl of aromatic aldehydes towards by attack 1-(tertbutyldimethylsilyloxy)-1-methoxyethene to form the expected silyl protected β-hydroxyesters. In these complexes, the η5-η3 haptotropic shift of the indenyl ligand, have shown to undergo this shift 100 times faster than their cyclopentadienyl (Cp) analogues. Accordingly, a noticeable increase in catalytic activity was observed in the Mukaiyama aldol reaction upon exchange of the Cp ligand for the Ind ligand
Lenze, Matthew Joseph, "The Investigation of Iron(II) Complexes and Their Catalytic Applications" (2013). Dissertations. 308.