We report on the synthesis and structure, as well as on the mechanism of formation of the [Ge -CH=CH-CH=CH-Ge ] unit. As shown by in situ NMR spectroscopy ( H, COSY, HSQC, HMBC), both (1Z,3Z)- and (1E,3Z)-[Ge -CH=CH-CH=CH-Ge ] are formed during the reaction of a mixture of 1,4-bis(trimethylsilyl)butadiyne and A Ge (A=K, Rb) with ethylenediamine. However, upon layering of the obtained solution with 222-crypt/toluene (222-crypt=4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-[8.8.8]hexacosan) only the (1Z,3Z)-isomer crystallizes as {[A(222-crypt)] [(1Z,3Z)-(Ge -CH=CH-CH=CH-Ge )]}(tol) (en) (A=K, Rb) salts. Single crystals of these salts were characterized by X-ray structure analysis and Raman spectroscopy, indicating the presence of three superimposed conformers of (1Z,3Z)-[Ge -CH=CH-CH=CH-Ge ] , which show different orientations of the cluster units with respect to the planar (1Z,3Z)-buta-1,3-dien-1,4-diyl linker unit.
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