Density functional theory (B3LYP//6-311+G*) calculations including Poisson-Boltzmann implicit solvent and NMR were used to study the formation of a series of para-substituted triphenylboroxine, amine adducts with respect to their phenylboronic acid monomers and free amine in solution. Our calculations suggest that the intermediate prior to forming trimer, amine is a dimer, amine adduct. Formation of dimer, amine can proceed via two pathways. Electron-donating substituents favor dimerization of two monomers before addition of the amine, and electron-withdrawing substituents favor formation of a monomer, amine adduct before addition of the second monomer. We also find that pi-electron acceptors destabilize formation of the dimer and trimer with respect to its monomers. Electron-withdrawing substituents favor adduct formation. Adduct formation is enthalpically stabilized by increasing the polarity of the solvent but differential solubility of the monomer compared to trimer, amine also has an effect on the equilibrium constant.