Concepedia

Publication | Closed Access

Acylation of Homoatomic Ge<sub>9</sub> Cages and Subsequent Decarbonylation

DOI

25

Citations

34

References

2018

Year

Sabine Frischhut, Wilhelm Klein, Markus Drees, Thomas F. Fässler
Chemistry - A European Journal

Abstract

The direct acylation of Ge<sub>9</sub> Zintl clusters by the reaction of K[Ge<sub>9</sub> {Si(SiMe<sub>3</sub> )<sub>3</sub> }<sub>3</sub> ] with acyl chlorides in hexane or toluene solutions is presented, leading to the neutral, carbonyl-derivatized products [{Si(SiMe<sub>3</sub> )<sub>3</sub> }<sub>3</sub> Ge<sub>9</sub> (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<sub>9</sub> Zintl clusters. [{Si(SiMe<sub>3</sub> )<sub>3</sub> }<sub>3</sub> Ge<sub>9</sub> (CO)tBu] readily releases CO at ambient conditions under formation of [{Si(SiMe<sub>3</sub> )<sub>3</sub> }<sub>3</sub> Ge<sub>9</sub> tBu]. This temperature-dependent decarbonylation most likely proceeds via a radical Norrish-type I α-bond cleavage. Except for R'=tBu and Bz all obtained acyl-derivatized Ge<sub>9</sub> cluster compounds do not release CO even at elevated temperatures. All compounds were characterized by NMR spectroscopy. [{Si(SiMe<sub>3</sub> )<sub>3</sub> }<sub>3</sub> Ge<sub>9</sub> (CO)R'] (R'=tBu, Ph, Me, iPr) as well as [{Si(SiMe<sub>3</sub> )<sub>3</sub> }<sub>3</sub> Ge<sub>9</sub> tBu] were further structurally characterized by single crystal X-ray diffraction.

References

YearCitations

Page 1