New syntheses of complexes containing the recently discovered (N(2))(3-) radical trianion have been developed by examining variations on the LnA(3)/M reductive system that delivers "LnA(2)" reactivity when Ln = scandium, yttrium, or a lanthanide, M = an alkali metal, and A = N(SiMe(3))(2) and C(5)R(5). The first examples of LnA(3)/M reduction of dinitrogen with aryloxide ligands (A = OC(6)R(5)) are reported: the combination of Dy(OAr)(3) (OAr = OC(6)H(3)(t)Bu(2)-2,6) with KC(8) under dinitrogen was found to produce both (N(2))(2-) and (N(2))(3-) products, (ArO)(2)Dy(THF)(2)(μ-η(2):η(2)-N(2)), 1, and (ArO)(2)Dy(THF)(μ-η(2):η(2)-N(2))[K(THF)(6)], 2a, respectively. The range of metals that form (N(2))(3-) complexes with N(SiMe(3))(2) ancillary ligands has been expanded from Y to Lu, Er, and La. LnN(SiMe(3))(2)/M reactions with M = Na as well as KC(8) are reported. Reduction of the isolated (N(2))(2-) complex {(Me(3)Si)(2)NY(THF)}(2)(μ-η(2):η(2)-N(2)), 3, with KC(8) forms the (N(2))(3-) complex, {(Me(3)Si)(2)NY(THF)}(2)(μ-η(2):η(2)-N(2))[K(THF)(6)], 4a, in high yield. The reverse transformation, the conversion of 4a to 3 can be accomplished cleanly with elemental Hg. The crown ether derivative {(Me(3)Si)(2)NY(THF)}(2)(μ-η(2):η(2)-N(2))[K(18-crown-6)(THF)(2)] was isolated from reduction of 3 with KC(8) in the presence of 18-crown-6 and found to be much less soluble in tetrahydrofuran (THF) than the K(THF)(6) salt, which facilitates its separation from 3. Evidence for ligand metalation in the YN(SiMe(3))(2)/KC(8) reaction was obtained through the crystal structure of the metallacyclic complex {(Me(3)Si)(2)NY[CH(2)Si(Me(2))NSiMe(3)]}[K(18-crown-6)(THF)(toluene)]. Density functional theory previously used only with reduced dinitrogen complexes of closed shell Sc(3+) and Y(3+) was extended to Lu(3+) as well as to open shell 4f(9) Dy(3+) complexes to allow the first comparison of bonding between these four metals.