Contrasting Bonding Extremes in Two [Ge6] n− Complexes: A Wadian Polyhedron (n = 2) versus a Hydrocarbon-like 2c–2e Polygermanide (n = 12)

[Nb­(η6-C6H3Me3)2] reacts with ethylenediamine (en) solutions of K4Ge9 in the presence of 18-crown-6 to give [(η6-C6H3Me3)­NbHGe6]2– (1) and [(η6-C6H3Me3)­NbGe6Nb­(η6-C6H3Me3)]2– (2) as their corresponding [K­(18-crown-6)]+ salts. The crystalline solids are dark brown, air-sensitive, and sparingly soluble or insoluble in most solvents. The [K­(18-crown-6)]+ salts of cluster ions 1 and 2 have been characterized by energy-dispersive X-ray (EDX) analysis, NMR studies, single-crystal X-ray diffraction, and electrospray ionization time-of-flight (ESI-TOF) mass spectrometry studies. Cluster ions 1 and 2 have markedly different [Ge6] moieties: an electron-deficient carborane-like subunit in 1 and a two-center, two-electron cyclohexane-like subunit in 2.