The 1,1′-diaminoferrocene derivatives [Fe(η5-C5H4–NHAd)2] (Ad=2-adamantyl) and [Fe(η5-C5H4–NHtBu)2] were investigated in terms of their suitability for the synthesis of N-heterocyclic tetrylenes of the type [{Fe(η5-C5H4–NR)2}E] (E=Ge, Sn). The synthesis of these target compounds was easily achieved with R=tBu, but failed with R=Ad. In the latter case, the stannylene was not sufficiently stable for isolation and decomposed to the aminoiminoferrocene derivative [Fe(η5-C5H4–NHAd)(η5-C5H4–N=Ad′)] (Ad′=adamant-2-ylidene). Attempts to synthesise [{Fe(η5-C5H4–NAd)2}Ge] afforded intractable material, from which the unusual compound [μ2-{Fe(η5-C5H4–NAd)2}Ge2(μ3-O)(GeCl2)] was obtained by serendipity. It contains GeO, stabilised by adduct formation with GeCl2 and the target germylene. [Fe(η5-C5H4–NHtBu)2], [Fe(η5-C5H4–NHAd)2], [Fe(η5-C5H4–NHAd)(η5-C5H4–N=Ad′)], [μ2-{Fe(η5-C5H4–NAd)2}Ge2(μ3-O)(GeCl2)] and [{Fe(η5-C5H4–NtBu)2}E] (E=Ge, Sn) were structurally characterised by single-crystal X-ray diffraction.