[((BuNH)-Bu-t)Te(mu-(NBu)-Bu-t)(2)Te((NBu)-Bu-t)][OSO2CF3] (4a) is obtained in quantitative yields by the treatment of [((BuN)-Bu-t)-Te(mu-(NBu)-Bu-t)(2)Te((NBu)-Bu-t)] (1) with HCF3SO3. The reaction of 4a with Lil and iodine in the molar ratio 11:4.5 affords a product that, upon recrystallization from acetonitrile, was found to be a solid solution of [((BuNH)-Bu-t)Te(mu-(NBu)-Bu-t)(2)-Te((NBu)-Bu-t)](2)](20) (5a) and [((BuNH)-Bu-t)Te(mu-(NBu)-Bu-t)(2)Te((NHBu)-Bu-t)](2)](18) (5b). Consequently, the crystal structure is disordered, containing 88.3(1)% of 5a(.)2MeCN and 11.7(1)% of 5b(.)2MeCN. The l(20) framework is involved in two symmetry-equivalent N-l-l-l-l fragments, two l(3)(-) ions, and three l(2) molecules that are linked together by l(...)l secondary bonding interactions. The bonding in the N-l-l-l-l fragment can be considered in terms of the lp(N) -> sigma*(l(2)) and pi*(l(2)) -> sigma*(l(2)) charge-transfer interactions involving one [((BuNH)-Bu-t)Te(mu-(NBu)-Bu-t)(2)Te((NBu)-Bu-t)](+) cation and two 12 units. The N-l bond length of 2.131(7) angstrom, the 1-1 distances of 3.118(1), 3.095(2), and 2.788(2) angstrom, and the angle l(2)-l(2) angle of 84.75(4)degrees are consistent with this bonding scheme. The l-l bond distances in the two symmetry-equivalent 13 ions are 3.113(1) and 2.792(2) angstrom, and those in two crystallographically independent 12 molecules are 2.736(2) and 2.743(1) angstrom. The formal l(18)(4-) anion in 5b(.)2MeCN consists of four l(3)(-) anions and three 12 molecules linked by l(...)l secondary bonds. One crystallographically independent l(3) anion is connected to the [((BuNH)-Bu-t)Te(mu-(NBu)-Bu-t)(2)-Te((HNBu)-Bu-t)](2+) cation by two hydrogen bonds [H(...)l = 2.823(5) and 2.983(5) angstrom; N(...)l = 3.697(8) and 3.857(9) angstrom]. The 13 anions and 12 molecules in 5b show virtually identical bond parameters to those in 5a. The treatment of 1 with iodine and the reactions of its methylated derivatives, [((BuNMe)-Bu-t)Te(mu-(NBu)-Bu-t)(2)Te((NBu)-Bu-t)][OSO2CF3] and [((BuNMe)-Bu-t)-Te(mu-(NBu)-Bu-t)(2)Te((MeNBu)-Bu-t)][OSO2CF3](2), with Lil and iodine also afford highly moisture-sensitive polyiodides, either by the formation of N-l charge-transfer complexes or by ionic interactions. The crystal structures of the partially hydrolyzed products, [((t)BulN)Te(mu-(NBu)-Bu-t)(2)Te(mu-O)](2)(l(3))(2) (3), [((BuMeN)-Bu-t)Te(mu-(NBu)-Bu-t)(2)Te(mu-O)](2)(l(3))(2) (6), and 6(.)2MeCN, are also reported.