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

[Nb(eta(6)-C6H3Me3)(2)] reacts with ethylenediamine (en) solutions of K4Ge9 in the presence of 18-crown-6 to give [(eta(6)-C6H3Me3)NbHGe6](2-) (1) and [(eta(6)-C6H3Me3)NbGe6Nb(eta(C6H3Me3)-C-6)](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 energydispersive 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 [Ge-6] moieties: an electron-deficient carborane-like subunit in 1 and a two-center, two-electron cyclohexane-like subunit in 2.

Automated summary

The reaction of [Nb(eta(6)-C6H3Me3)(2)] with ethylenediamine and K4Ge9 in the presence of 18-crown-6 yielded two cluster ions, 1 and 2, with distinct [Ge-6] motifs. These crystalline solids are dark brown, air-sensitive, and sparingly soluble or insoluble in most solvents. Characterization of cluster ions 1 and 2 was done through various techniques, revealing the presence of an electron-deficient carborane-like subunit in 1 and a two-center, two-electron cyclohexane-like subunit in 2.