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Synthesis and Structure of Cyclotrigermenium Salts of Tetrakis{3,5‐bis(trifluoromethyl)phenyl}borate, Tetrakis(pentafluorophenyl)borate and Tetrakis{4‐[ tert ‐butyl(dimethyl)silyl]‐2,3,5,6‐tetrafluorophenyl}borate: A Stable Free Germyl Cation in the Condensed Phase
Author(s) -
Sekiguchi Akira,
Fukaya Norihisa,
Ichinohe Masaaki,
Ishida Yutaka
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200006)2000:6<1155::aid-ejic1155>3.0.co;2-c
Subject(s) - chemistry , trifluoromethyl , dichloromethane , chloroform , boron , medicinal chemistry , toluene , counterion , benzene , tris , diethyl ether , trifluoromethylation , solvent , acetonitrile , inorganic chemistry , borylation , ion , organic chemistry , alkyl , biochemistry , aryl
The reaction of tetrakis(tri‐ tert ‐butylsilyl)cyclotrigermene ( 1a ) with Ph 3 C + [3,5‐(CF 3 ) 2 C 6 H 3 ] 4 B − (TFPB − ), Ph 3 C + (C 6 F 5 ) 4 B − (TPFPB − ), and Ph 3 C + [4‐( t BuMe 2 Si)C 6 F 4 ] 4 B − (TSFPB − ) in benzene produced the stable free tris(tri‐ tert ‐butylsilyl)cyclotrigermenium ion ( 2a + ) with the corresponding tetraarylborate as the counterion. The crystal structures of 2a + TFPB − and 2a + TSFPB − reveal a free germyl cation with a two π‐electron system. The three‐membered ring of germanium atoms constitutes an almost equilateral triangle. The cyclotrigermenium tetraarylborates, 2a + TFPB − , 2a + TPFPB − , and 2a + TSFPB − , are stable in solution. The spectroscopic data show that 2a + is a free germyl cation, does not coordinate to either the solvent molecules (dichloromethane, chloroform, toluene, or diethyl ether) or the counter anions (TFPB − , TPFPB − , or TSFPB − ). The tris(tri‐ tert ‐butylgermyl)cyclotrigermenium ion ( 2b + ) was also characterized.