The finding that dioxygen binds end-on to the CuB site in the crystal structure of a precatalytic complex of peptidylglycine α-hydroxylating monooxygenase has spurred the search for biomimetic model complexes exhibiting the same dioxygen coordination. Recent work has not only indicated that sterically hindered β-diketiminate ligands (L1) could support side-on 1: 1 Cu-O2 adducts, but also that an end-on L1Cu(THF)O2 structure occurs as an unstable intermediate in the oxygenation mechanism of the Cu(i) complex. In this work, density functional theory and multireference methods are used to determine the potential of ancillary ligands, X, other than THF to yield thermodynamically stable end-on L1CuXO2 species. A diverse set of ligands X, comprising phosphines, thiophene, cyclic ethers, acetonitrile, para-substituted pyridines, N-heterocyclic carbenes, and ligands bearing hydrogen bond donors, has been considered in order to identify ligand characteristics which energetically favor end-on L1CuXO2 over: a) reversion to the Cu(i) complex and dioxygen, b) isomerization to side-on L 1CuXO2, and c) decay to L1CuO2 and X. Ancillary ligands with judiciously chosen degrees and orientation of steric bulk and which bear potential hydrogen bond donors to an end-on bound dioxygen moiety most favor oxygenation of L1CuX to yield end-on L 1CuXO2. Conversion to the side-on isomer can be deterred through the use of a sufficiently bulky ligand X, such as one that is at least the size of a 5-membered ring. Loss of X to give L1CuO2 can be made prohibitively endergonic by employing ligands X which are highly electron donating and which backbond strongly with and σ-donate significantly to copper.