Deprotonated N,N'-disubstituted 1,8-diaminonaphthalenes (R(2)DAN(2-); R = (CH3)(2)CH, C6H5, 3,5-Me2C6H3) were incorporated into Ta(V) complexes employing two methods. The direct proton transfer reaction of the parent amine, 1,8-(RNH)(2)C10H6, with TaMe3Cl2 led to elimination of methane and formation of TaCl3[1,8-(RN)(2)C10H6] (1, 2). Reaction of the dilithiated amido species, Li(2)R(2)DAN, with TaMe3Cl2 or [Ta(NEt2)(2)Cl-3] yielded TaMe3-[1,8-(RN)(2)C10H6] (3, 4) and TaCl(NEt2)(2)[1,8-(RN)(2)C10H6] (5, 6), respectively. X-ray structural studies of these complexes revealed the flexible coordination behavior of R(2)DAN(2-) by demonstrating that the ligand bonded to Ta with a coordination array dependent on the identity of the other ligands bonded to tantalum. Computational analysis of these complexes confirmed that the energetic components for binding of R(2)DAN(2-) to these TaX32+ fragments were dominated by the electronic features of the metal fragment. Chemical transformations of the bound ligand were evaluated by reaction of compounds 5 and 6 with LiNMe2 and MeLi. Simple metathesis products Ta(NEt2)(2)NMe2-[1,8-((PrN)-Pr-i)(2)C10H6](R = Pr-i 7, 9 = 3,5-Me-2(C6H3) 8) were obtained from reactions with LiNMe2. In contrast, when the R group of the DAN ligand was Pr-i, reaction with MeLi ultimately led to activation of the isopropyl group and formation of the metallaziridine [kappa(3)-(Me2CN)((PrN)-Pr-i)C10H6]Ta(NEt2)(2) (9) species via the elimination of methane.