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A Combined 1 H/ 6 Li NMR DOSY Strategy Finally Uncovers the Structure of Isopropyllithium in THF
Author(s) -
BarozzinoConsiglio Gabriella,
Hamdoun Ghanem,
Fressigné Catherine,
HarrisonMarchand Anne,
Maddaluno Jacques,
Oulyadi Hassan
Publication year - 2017
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.201702990
Subject(s) - dimer , monomer , chemistry , solvation , reactivity (psychology) , reagent , computational chemistry , nuclear magnetic resonance spectroscopy , molecule , stereochemistry , organic chemistry , polymer , medicine , alternative medicine , pathology
Abstract Despite its common use in synthesis, the structure of isopropylliyhium in THF has never been determined, a dimer being generally proposed but not supported. This paper fills this data gap through a sophisticated NMR study that shows that, in THF at low‐temperature, isopropyllithium is in the form of a 1:2 mixture of a trisolvated monomer and a disolvated dimer in equilibrium. The presence of the monomer, never evoked before, together with a hypo‐solvation of the dimer hinted by DFT calculations, provides a rational explanation to the remarkable reactivity of this organolithium reagent in ethereal solvents.