Synthesis, functionalization, and coordination of bulky m-terphenyls and [Beta]-diketiminates

Abstract

The synthesis of m-terphenyl iodide and m-terphenyl carboxylic acid was performed and described. A large scale, low-cost synthesis was developed for m-terphenyl iodide that reduced the number of steps and time required to obtain the material. The subsequent conversion to 2,6-dimesitylbenzoic acid was performed and coordination of the carboxylate anion to cationic lithium was done and structurally characterized by X-ray crystallography.

Spartan '06 calculations of a boron ylidene at the MP2/6-31G* level suggest that the addition of an electron-donating group to β-diketiminate increases the singlet-triplet energy gap. The one-pot synthesis of the modified β-diketiminate was successful using the precusor [Me₂NC(Cl)CHC(Cl)NMe₂⁺][HCl₂⁻] followed by in situ quenching with aniline. Coordination of the new ligand [Me₂NC(=NPh)CHC(=NPh)NMe₂]⁻ to -AlMeCl illustrated its capability to have similar properties to the β-diketiminate.