Premium
Silyl Anions or Silylenoids?—A DFT Study of Silyllithium Compounds with π‐Donating Substituents
Author(s) -
Flock Michaela,
Marschner Christoph
Publication year - 2005
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.200401353
Subject(s) - silylene , moiety , silylation , chemistry , tetrahedron , polar , molecule , gas phase , inversion (geology) , crystallography , tetrahedral molecular geometry , computational chemistry , stereochemistry , medicinal chemistry , silicon , organic chemistry , catalysis , physics , geology , paleontology , structural basin , astronomy
Geometry optimizations at the B3LYP/6‐31+G(d) level for a set of X(SiH 3 )MeSiLi molecules (X=F, OH, NH 2 , Cl, SH, and PH 2 ) show that the tetrahedral structure prevails in polar solutions; however, it readily isomerizes into a silylenoid with energy barriers of less than 15 kJ mol −1 . Inverted structures, which predominate in the gas phase, could not be located in solution. Configuration inversion is unfavorable, with energy barriers between 80 and 220 kJ mol −1 . The α elimination into a silylene moiety and the corresponding LiX is only likely to occur in solution, particularly for X=Cl and SH.