Germyl cations with Ge-S bond: an experimental and theoretical study on the gaseous F(n)Ge(SH)(3-n)+ (n=0-2).

The germyl cations F(2)Ge(SH)(+), FGe(SH)(2)(+) and Ge(SH)(3)(+) were obtained from ionized mixtures of GeF(4) and H(2)S. Ion trap mass spectrometry revealed the occurrence of three consecutive addition-HF elimination reactions between GeF(3)(+), F(2)Ge(SH)(+) and FGe(SH)(2)(+) and H(2)S. The structure and the mechanism of formation of the observed F(n)Ge(SH)(3-n)(+) (n = 0-2) were investigated by ab initio calculations performed at the MP2 and coupled cluster level of theory. It was also possible to note regular trends in the geometries and Lewis acidities of the F(n)Ge(SH)(3-n)(+) (n= 0-3).