Abstract
This paper gives an account on hypervalent fluoro- and chloro(pentafluoroethyl)germanium compounds. The selective synthesis of the tris(pentafluoroethyl)dichlorogermanate salt [PNP][(C2 F5 )3 GeCl2 ] as well as its X-ray structural analysis is described. As a representative example for pentafluoroethylfluorogermanates, the synthesis and structure of 2,4,6-triphenylpyryliumtris(pentafluoroethyl)difluorogermanate [C23 H17 O][(C2 F5 )3 GeF2 ] is reported. Fluoride-ion affinities for pentafluoroethylgermanes were calculated using quantum chemical methods, disclosing (C2 F5 )3 GeF as a weaker Lewis acid than (C2 F5 )3 SiF or (C2 F5 )3 PF2 . The theoretical results were confirmed by experiments and give the basis of a synthetic protocol for (C2 F5 )3 GeF. Pentakis(pentafluoroethyl)germanate [PPh4 ][Ge(C2 F5 )5 ] was detected as an intermediate during the synthesis of [PPh4 ][(C2 F5 )4 GeF] starting from tris(pentafluoroethyl)difluorogermanate and LiC2 F5 .
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