[1.1]Ferrocenophanyllithium (1) is shown by dynamic NMR (DNMR) and isotopic perturbation to undergo a rapid intramolecular 1,12-proton transfer coupled with 1,12-lithium ion transfer. The first [C-H-C](-) hydrogen bond previously reported to be present in 1 is shown by X-ray crystallography to be absent in the solid state. The C-13 NMR spectrum of the bridge-labeled compound [1,12-C-13(2)][1.1]ferrocenophanyl[1-Li-6]lithium (6) in 2,5-dimethyltetrahydrofuran (DMTHF) displays a 1:1:1 triplet ((1)J(C-13, Li-6) = 4.0 Hz) showing that Li-6 is bonded to C-1 and that 1 is monomeric. Transient nuclear Overhauser effects (tNOE’s) measured in DEE-d(10) in bridged monodeuterated 1 show that the bridges in 1 are syn and not anti to each other and that lithium is exo-coordinated to the anionic bridge carbon. The (1)J(C-13, H-1) coupling constants show that the hybridization of the carbanionic carbon is intermediate between sp(2) and sp(3). Thus the solution and solid state structures of 1 are similar. UV-vis spectroscopy shows that 1 exists mainly as contact ion pairs (CLPs) in the temperature range -100 to +25 degrees C in THF, DMTHF, and diethyl ether (DEE). In dimethoxyethane (DME), 1 is mainly CIPs above +25 degrees C but is mainly separated ion pairs (SIPs) below -30 degrees C.