X-ray crystallographic NMR and calculational modeling studies using B3LYP/6-311G* of selected dilithium derivatives of the 1,3-butadiene dianion including cis-dilithio-1,4-bis(TMS)-2-butene·(TMEDA)(2)2, internally solvated cis-dilithio-1,4-bis[bis(2-methoxyethyl)aminomethyldimethylsilyl]-2-butene 5, and using only modeling, 1,4-dilithio-2-butene·(TMEDA)(2)9 reveal remarkably similar structural and NMR parameters. In the solid, 5 consists of unusual "T" shaped dynamic clusters. In all three bridging lithiums are sited between 1.8 and 1.9 Å normal to the centroids of opposite faces of the near coplanar of the 2-butene component. Typical bond lengths of the latter are 1.458 ± 0.004, 1.385 ± 0.006, and 1.459 ± 0.003 Å, for C1-C2, C2-C3, and C3-C4, respectively. The (13)C chemical shifts lie within the ranges δ 21 ± 0.5, 99 ± 0.7, 99 ± 0.7 and 21 ± 0.5 for C1, C2 and C3 together, and C4, respectively. Dynamic (13)C NMR provides activation parameters for nitrogen inversion in 2 and 5, overall molecular inversion of 5, and conformational interconversion of 2.