Studies on the Reactivity of [Ge 9 ] 4− towards [Fe(cot)(CO) 3 ]: Synthesis and Characterization of [Ge 8 Fe(CO) 3 ] 3− and of the Anionic Organometallic Species [Fe(cot)(CO) 3 ] −

Reaction of cyclooctatetraene (COT) iron(II) tricarbonyl, [Fe(cot)(CO) 3 ], with one equivalent of K 4 Ge 9 in ethylenediamine (en) yielded the cluster anion [Ge 8 Fe(CO) 3 ] 3− which was crystallographically‐characterized as a [K(2,2,2‐crypt)] + salt in [K(2,2,2‐crypt)] 3 [Ge 8 Fe(CO) 3 ]. The chemically‐reduced organometallic species [Fe(η 3 ‐C 8 H 8 )(CO) 3 ] − was also isolated as a side‐product from this reaction as [K(2,2,2‐crypt)][Fe(η 3 ‐C 8 H 8 )(CO) 3 ]. Both species were further characterized by EPR and IR spectroscopy and electrospray mass spectrometry. The [Ge 8 Fe(CO) 3 ] 3− cluster anion represents an unprecedented functionalized germanium Zintl anion in which the nine‐atom precursor cluster has lost a vertex, which has been replaced by a transition‐metal moiety.