In this work, we use density functional theory calculations with a hybrid exchange-correlation functional and effective core pseudopotentials to determine the geometry of bare and phosphine-protected Au nanoclusters and characterize their electronic structure. Au clusters were bonded to four and eight PH ligands in order to evaluate the effect of ligand concentration on the electronic structure, while different positional configurations were also tried for four ligands attached to the cluster. We show that the neutral clusters become more nucleophilic as the ligands bind to the clusters at stable sites. The ground-state planar configuration of Au is maintained depending on the concentration and position of ligands. The effect of ionizing to the +2 charge state results in disruption of planar geometry in some cases because of inoccupation of a molecular orbital with the Au-Au bonding character. Natural bond order charge analyses showed that Au atoms oxidize upon ionization, instead of phosphine. The net positive charge makes the clusters more electrophilic with a capacity to absorb electrons from nucleophiles depending on the concentration and position of ligands and on the concentration of low-coordinated gold atoms. Besides, ionization energies and electron affinities were calculated through different mechanisms, finding that both variables are much higher for charged systems and change inversely with the concentration of ligands.