Abstract: Reaction of the Lewis acid Ga[N(C₆F₅)₂]₃ with acetonitrile and pyridine in toluene solution was characterized by ¹⁹F NMR. Quantum chemical calculations show that the shorter donor-acceptor bond in the acetonitrile complex is weaker by 73 kJ/mol than the longer donor-acceptor bond in the pyridine complex, which is consistent with partial dissociation of the Ga[N(C₆F₅)₂]₃·MeCN complex in toluene.