Density functional theory (DFT) and ab initio (Hartree-Fock) calculations employing the 6-31G* basis set are used to determine gas-phase proton microaffinities (PA(n,i)) of two bulky symmetrical tripodal tetraamine ligands N[(CH2)(4)NH2]3, trbn, and N[(CH2)(5)NH2]3, trpa. The corresponding proton macroaffinities (PA(n)) are calculated not only according to our recently established method but also considering two alternative formulas based on a Boltzmann distribution. The successive protonation macroconstants in aqueous solution for these bulky amines are predicted from the well-defined correlation between the calculated proton macroaffinities, without considering Boltzmann distribution, and the corresponding log Kn for these amines. The overall protonation constants are also predicted by two different methods.