GERMANIUM-CONTAINING HETEROBICYCLIC 10-PI-ELECTRON RING-SYSTEMS - SYNTHESIS AND CHARACTERIZATION OF NEUTRAL AND CATIONIC GERMANIUM(II) DERIVATIVES OF AMINOTROPONIMINATES

The neutral and cationic aminotroponiminate derivatives of germanium(I I)) have been investigated. The treatment of GeCl2 .(1,4-dioxane) with [(i-Pr)(2)ATI]Li or [(Me)(2)ATI]Li in a 1:1 molar ratio gave the corr esponding monochloro germanium(II) complex. Substitution of the chlori de ion of [(i-Pr)(2)ATI]GeCl with weakly coordinating anions [CF3SO3]( -) and [(eta(5)-C-5 H-5)ZrCl2(mu-Cl)(3)ZrCl2(eta(5)-C5H5)](-) led to c ationic germanium(II) species containing {[(i-Pr)(2)ATI]Ge}(+) ion. Al though NMR data of the cationic species show notable differences relat ive to their neutral analog, the solid state data show only minor chan ges in the C7N2Ge moiety. The Ge-N bond distances of the cations are n ot indicative of significant Ge-N pi-bonding. These compounds feature some of the smallest N-Ge-N angles known for Ge(II) compounds. Attempt ed synthesis of the tetraphenylborate salt of {[(Me)(2)ATI]Ge}(+) led to a phenyl group transfer product [(Me)(2)ATI]GePh . BPh3 with a Ge(I I)-B bond. Details of the H-1, C-13 NMR spectroscopy and X-ray crystal structures of all these compounds are described.