2,4-Disila-1-germatricyclo[2.1.0.0(2,5)]pentane: a new type of cage compound of group 14 elements with an extremely long Ge-C bridge bond and an "Umbrella"-type configuration of a Ge atom

J Am Chem Soc. 2002 Aug 28;124(34):9962-3. doi: 10.1021/ja020574z.

Abstract

The thermolysis of 1,1,2,3-tetrakis[di-tert-butyl(methyl)silyl]-4-phenyl-1,2-disila-3-germacyclopenta-2,4-diene 1 at 175 degrees C results in the quantitative formation of 1,2,3,4-tetrakis[di-tert-butyl(methyl)silyl]-5-phenyl-2,4-disila-1-germatricyclo[2.1.0. 02,5]pentane 2, representing a new type of cage compound of group 14 elements. The crystal structure of 2 was established by X-ray crystallography, which showed an extremely long Ge-C bridge bond of 2.242(3) A and an "umbrella"-type configuration of the Ge atom. The compound 2 readily reacted with benzaldehyde to produce 1,4,5,7-tetrakis[di-tert-butyl(methyl)silyl]-3,6-diphenyl-2-oxa-1,4-disila-5-germabicyclo[2.2.1]hept-5-ene 3 with an endocyclic Ge=C double bond.