Acylation of Homoatomic Ge Cages and Subsequent Decarbonylation.

The direct acylation of Ge Zintl clusters by the reaction of K[Ge {Si(SiMe ) } ] with acyl chlorides in hexane or toluene solutions is presented, leading to the neutral, carbonyl-derivatized products [{Si(SiMe ) } Ge (CO)R'] (R'=Me, iPr, tBu, Ph, Bz, cyclopropylmethyl, phenethyl, 4-vinylphenyl). This reaction is applicable to a wide range of acyl chlorides and allows for diverse functionalization of Ge Zintl clusters. [{Si(SiMe ) } Ge (CO)tBu] readily releases CO at ambient conditions under formation of [{Si(SiMe ) } Ge tBu].

Synthesis of low-oxidation-state germanium clusters comprising a functional anchor group - synthesis and characterization of [(Ge)(Ge-R)(Ge-(CH)-CH[double bond, length as m-dash]CH)] with R = Si(SiMe).

The first alkenyl-functionalized, uncharged deltahedral germanium clusters [{Si(SiMe)}Ge(CH)CH[double bond, length as m-dash]CH] (n = 1 or 3) comprising five Ge atoms are presented. All compounds were NMR-spectroscopically and mass-spectrometrically characterized. [{Si(SiMe)}Ge(CH)CH[double bond, length as m-dash]CH] was further characterized by X-ray structure analysis and Raman spectroscopy.

On the Mechanism of Connecting Deltahedral Zintl Clusters via Conjugated Buta-1,3-dien-1,4-diyl Functionalities: Synthesis and Structure of [Ge -CH=CH-CH=CH-Ge ].

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.

Synthesis of Zintl Triads Comprising Extended Conjugated π-Electronic Systems: [RGe-CH═CH-CH═CH-GeR] (R = -CH═CH, -C(CH)═CH-CH═N(CH)NH).

Triads with extended conjugated π-electronic systems between polyhedral cage molecules possess promising electronic properties. In contrast to the known fullerene-bridge-fullerene triads, fewer synthetic procedures are known for the related homoatomic deltahedral cage molecules of the heavier homologues of carbon. The synthesis of the organo-Zintl triads [RGe-CH═CH-CH═CH-GeR] with R = -CH═CH (R), -C(CH)═CH-CH═N(CH)NH ((2Z,4E)-7-amino-5-azahepta-2,4-dien-2-yl) (R) is reported, in which the deltahedral Ge cages carry an additional functional group, allowing for further connections.