In an effort to increase the overall efficiency of this synthesis,
we explored alternate amidation methods. Of the methods tried,
the most valuable involved carboxylate activation using
carbonyl diimidazole (CDI), as shown below.
This approach was found to be very clean, but separation of
the product from the solvent and by-products proved problematic. Ultimately however, it was found that the CMPO silane
reaction mixture could be used in the monolayer deposition
directly, with no ill side-effects on monolayer quality.
One method for enhancing selectivity for the larger actinide
cations over the more common transition metal cations is to
enlarge the chelating cavity of the ligand. Thus we also wanted
to prepare the corresponding homolog (structure 4). This was
accomplished via conjugate addition diethylphosphite to trifluoroethyl acrylate, as shown below. Once again, the trifluoroethyl ester was purified by vacuum distillation in good
yield.9 Mixing 4 with neat 2 resulted in a modest exotherm, and
was found to be complete in approximately 100 minutes. Once
again, attempted distillation resulted in partial decomposition of
the product, so the trifluoroethanol was removed under vacuum
and the desired CMPO silane (5) used directly