Iminophosphoranes or phosphazenes are an important class of compounds with increasing use in synthetic organic chemistry as neutral organic superbases exhibiting low nucleophilicity. Their electronic structure and therefore their properties strongly depend on substitution, but there have been very few theoretical studies devoted to this topic, and more specifically to the formation of electron donor acceptor complexes of iminophosphoranes with electrophiles. In this work, we have investigated the interaction with carbon dioxide at different ab initio levels. Carbon dioxide usually behaves as a Lewis acid and the reaction with iminiphosphoranes has been described as a nonconventional aza-Wittig process leading to isocyanates. The reaction can be conducted in supercritical CO2 conditions (carbon dioxide acts solvent and reactant), which is a promising strategy in the context of green chemistry. Our calculations have been carried out at the CCSD(T)/aug-ccpVTZ//MP2/aug-cc-pVTZ level for model systems and at the M06-2X/6-611+G(d,p) level for a larger species used in experiments. The electronic interactions and the interaction energies are analyzed and discussed in detail using the natural bond orbital method. Proton affinities and gas-phase basicities are provided as well.