Acylation of Homoatomic Ge-9 Cages and Subsequent Decarbonylation

作者：Frischhut Sabine; Klein Wilhelm; Drees Markus; Faessler Thomas F

来源：Chemistry - A European Journal, 2018, 24(36): 9009-9014.

DOI：10.1002/chem.201802318

• acylation
• functionalization
• germanium clusters
• radical decarbonylation
• Zintl

The direct acylation of Ge-9 Zintl clusters by the reaction of K[Ge-9{Si(SiMe3)(3)}(3)] with acyl chlorides in hexane or toluene solutions is presented, leading to the neutral, carbonyl-derivatized products [{Si(SiMe3)(3)}(3)Ge-9(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-9 Zintl clusters. [{Si(SiMe3)(3)}(3)Ge-9(CO)tBu] readily releases CO at ambient conditions under formation of [{Si(SiMe3)(3)}(3)Ge(9)tBu]. This temperature-dependent decarbonylation most likely proceeds via a radical Norrish-typeI alpha-bond cleavage. Except for R'=tBu and Bz all obtained acyl-derivatized Ge-9 cluster compounds do not release CO even at elevated temperatures. All compounds were characterized by NMR spectroscopy. [{Si(SiMe3)(3)}(3)Ge-9(CO)R'] (R'=tBu, Ph, Me, iPr) as well as [{Si(SiMe3)(3)}(3)Ge(9)tBu] were further structurally characterized by single crystal X-ray diffraction.

• 出版日期2018-6-26