Premium
A Neutral Germanium/Phosphorus Frustrated Lewis Pair and Its Contrasting Reactivity Compared to Its Silicon Analogue
Author(s) -
Kinder Timo A.,
Pior René,
Blomeyer Sebastian,
Neumann Beate,
Stammler HansGeorg,
Mitzel Norbert W.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901068
Subject(s) - adduct , germanium , reactivity (psychology) , chemistry , frustrated lewis pair , intramolecular force , silicon , crystallography , lewis acids and bases , stereochemistry , phosphorus , medicinal chemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
Chlorogermane (C 2 F 5 ) 3 GeCl with very electronegative pentafluoroethyl groups was converted with LiCH 2 P( t Bu) 2 to obtain the intramolecular frustrated Lewis pair (FLP) (C 2 F 5 ) 3 GeCH 2 P( t Bu) 2 , a neutral, germanium‐based FLP. Its reactivity was compared to its silicon homologue (C 2 F 5 ) 3 SiCH 2 P( t Bu) 2 . Both FLPs cleave NO but give cyclic (Si) and open‐chain oxides (Ge). In reactions with HCl both FLPs gave the same adduct type in the solid state, while the proton seems more mobile in solution in the germanium case. Reactions with PhCNO and Me 3 SiCHN 2 result in ring‐type adducts. The structures of (C 2 F 5 ) 3 GeCH 2 P( t Bu) 2 and of five adducts with substrates were elucidated by X‐ray diffraction. The study clearly showed the germanium compound to have a more moderate Lewis acidity compared to the silicon analogue.