In an attempt to prepare new Fe catalysts for the dehydrocoupling of amine-boranes and to provide mechanistic insight, the paramagnetic FeII dimeric complex [Cp'FeI]2 (1) (Cp'=η5 -((1,2,4-tBu)3 C5 H2 )) was used as a precursor to a series of cyclopentadienyl FeII and FeIII mononuclear species. The complexes prepared were [Cp'Fe(η6 -Tol)][Cp'FeI2 ] (2) (Tol=C6 H5 Me), [Cp'Fe(η6 -Tol)][BArF4 ] (3) (BArF4 =[B(C6 H3 (m-CF3 )2 )4 ]- ), [N(nBu)4 ][Cp'FeI2 ] (4), Cp'FeI2 (5), and [Cp'Fe(MeCN)3 ][BArF4 ] (6). The electronic structure of the [Cp'FeI2 ]- anion in 2 and 4 was investigated by SQUID magnetometry, EPR spectroscopy and ab initio Complete Active Space Self Consistent Field-Spin Orbit (CASSCF-SO) calculations, and the studies revealed a strongly anisotropic S=2 ground state. Complexes 1-6 were investigated as catalysts for the dehydrocoupling of Me2 NH⋅BH3 (I) in THF at 20 °C to yield the cyclodiborazane product [Me2 N-BH2 ]2 (IV). Complexes 1-4 and 6 were active dehydrocoupling catalysts towards I (5 mol % loading), however 5 was inactive, and ultra-violet (UV) irradiation was required for the reaction mediated by 3. Complex 6 was found to be the most active precatalyst, reaching 80 % conversion to IV after 19 h at 22 °C. Dehydrocoupling of I by 1-4 proceeded via formation of the aminoborane Me2 N=BH2 (II) as the major intermediate, whereas for 6 the linear diborazane Me2 NH-BH2 -NMe2 -BH3 (III) could be detected, together with trace amounts of II. Reactions of 1 and 6 with Me3 N⋅BH3 were investigated in an attempt to identify Fe-based intermediates in the catalytic reactions. The σ-complex [Cp'Fe(MeCN)(κ2 -H2 BH⋅NMe2 H][BArF4 ] was proposed to initially form in dehydrocoupling reactions involving 6 based on ESI-MS (ESI=Electrospray Ionisation Mass Spectroscopy) and NMR spectroscopic evidence. The latter also suggests that these complexes function as precursors to iron hydrides which may be the true catalytic species.