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The Solution Structure of (Me 3 Si) 3 CSiBr—An Ab Initio/NMR Study
Author(s) -
Flock Michaela,
Dransfeld Alk
Publication year - 2003
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.200304879
Subject(s) - silylene , ab initio , chemistry , crystallography , ab initio quantum chemistry methods , ion , silicon , nuclear magnetic resonance spectroscopy , computational chemistry , molecule , stereochemistry , organic chemistry
The first halosilylene stable in solution was investigated by ab initio/NMR calculations (IGLO SOS‐DFPT PW91/B2//B3LYP/6‐31+G(d)). The δ 29 Si calc of (Me 3 Si) 3 CSiBr (446 ppm) does not agree with the measured NMR signal at 106 ppm assigned to the free halosilylene. From the possible silylene complexes in the reaction solution, two structures agree with the observed NMR signal: the (Me 3 Si) 3 CSiBr 2 anion ( δ 29 Si calc =124 ppm) and the unsolvated and solvated complex of the anion with two Li + ( δ 29 Si calc =117 and estimated 134 ppm). Additionally the δ 29 Si calc of alkylsilylenes, R‐Si‐X, ranging from 200 to 900 ppm are presented to guide NMR identification in future silylene synthesis.