Abstract:

This dissertation describes the Ln(II) reduction reactivity of both isolated Ln(II) complexes containing (NR2)1− (R = SiMe3) amide ligands and in situ Ln(NR2)3/M reactions. The results show the diversity of products obtained by amide-based Ln(II) reduction due to subtle changes in reaction conditions. Chapter 1 outlines the reactions of isolated [GdII(NR2)3]1− with N,N-dicyclohexylcarbodiimide, CS2, S8, pyridine, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), MeCN, BiPh3, and SnPh4 in order to determine if the 4f75d1 configuration in Gd(II) in an isolated compound could reveal new reaction pathways. Chapter 2 outlines solvent decomposition reactions by Ln(NR2)3/K reactions with the smaller rare earth metals, Ln = Y, Ho, Er, and Lu. This Chapter provides more information on solvent reactivity in these reductive systems by describing a series of C–O cleavage products isolated from Ln(NR2)3/K reactions with ethers. Chapter 3 outlines the investigation of the reductive chemistry of cerium with in-situ Ce(NR2)3/M/N2 reactions. In this Chapter it is shown that crypt can function as a bidentate ligand to rare-earth ions. Chapter 4 outlines the reductive chemistry of neodymium with in-situ Nd(NR2)3/M/N2 reactions. Examination of the in-situ reduction of Nd(NR2)3 at low temperature in Et2O in the presence of 18-crown-6 provides a crystal system that demonstrates a solid-state isomerization of an end-on bound (N=N)2− moiety to side-on. This Chapter also describes a possible connection between the Ln(NR2)3/M reductions of N2 and reductions by isolated Ln(II) complexes.