Compounds of Germanium and Tin, 18. Cleavage Reactions of Hexa‐<i>tert</i>‐butylcyclotrigermane: Racemate versus Conglomerate Crystallization

Abstract

Abstract Treatment of hexa‐ tert ‐butylcyclotrigermane ( 3 ) with CCl 4 , Br 2 , and I 2 furnishes the correspondingly substituted 1,3‐dichloro‐ ( 4 ), 1,3‐dibromo‐ ( 5 ), and 1,3‐diiodotrigermanes ( 6 ). The symmetries of the molecules of 5 and 6 are very similar (point group C 1 ) revealing gauche‐anti conformations and different GeGe bond lengths. However, while 5 crystallizes as a racemate, 6 forms a conglomerate of enantiomerically pure crystals. The X‐ray structure analysis of the 1,3‐dimethyltrigermane ( 7 ) derivative, derived from 6 by a sequence of metalation and methylation reactions, reveals more symmetrical molecules of the point group C 2 which also crystallize as a racemate. Irradiation of 3 leads to tetra‐ tert ‐butyldigermene ( 8 ) and di‐ tert ‐butylgermylene ( 9 ) which could be trapped by addition and cycloaddition reactions with selenium, tellurium, and 3,5‐di‐ tert ‐butyl‐1,2‐benzoquinone.